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Articleshttpsdoiorg101038s41563-019-0562-6
Quantitative production of butenes from biomass-derived γ-valerolactone catalysed by hetero-atomic MFI zeoliteLongfei Lin 1 Alena M Sheveleva12 Ivan da Silva 3 Christopher M A Parlett 456 Zhimou Tang7 Yueming Liu7 Mengtian Fan1 Xue Han1 Joseph H Carter1 Floriana Tuna1 Eric J L McInnes 1 Yongqiang Cheng8 Luke L Daemen8 Svemir Rudić3 Anibal J Ramirez-Cuesta 8 Chiu C Tang6 and Sihai Yang 1
1Department of Chemistry and Photon Science Institute University of Manchester Manchester UK 2International Tomography Centre SB RAS and Novosibirsk State University Novosibirsk Russia 3ISIS Facility STFC Rutherford Appleton Laboratory Chilton UK 4School of Chemical Engineering and Analytical Science University of Manchester Manchester UK 5University of Manchester at Harwell Diamond Light Source Harwell Campus Didcot UK 6Diamond Light Source Harwell Science and Innovation Campus Didcot UK 7Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and Molecular Engineering East China Normal University Shanghai China 8The Chemical and Engineering Materials Division (CEMD) Neutron Sciences Directorate Oak Ridge National Laboratory Oak Ridge TN USA e-mail SihaiYangmanchesteracuk
SUPPLEMENTARY INFORMATION
In the format provided by the authors and unedited
NATuRE MATERIALS | wwwnaturecomnaturematerials
1
Supplementary Information
Quantitative production of butenes from biomass-derived γ-valerolactone
catalysed by hetero-atomic MFI zeolite
Longfei Lin1 Alena M Sheveleva12 Ivan da Silva3 Christopher M A Parlett456 Zhimou Tang7 Yueming
Liu7 Mengtian Fan1 Xue Han1 Joseph H Carter1 Floriana Tuna1 Eric J L McInnes1 Yongqiang Cheng8
Luke L Daemen8 Svemir Rudić3 Anibal J Ramirez-Cuesta8 Chiu C Tang6 and Sihai Yang1
1 School of Chemistry and Photon Science Institute University of Manchester Manchester M13 9PL (UK)
2 International Tomography Center SB RAS and Novosibirsk State University Novosibirsk 630090
(Russia)
3 ISIS Facility STFC Rutherford Appleton Laboratory Chilton Oxfordshire OX11 0QX (UK)
4 School of Chemical Engineering and Analytical Science University of Manchester Manchester M13 9PL
(UK)
5 University of Manchester at Harwell Diamond Light Source Harwell Campus Didcot Oxfordshire
OX11 0DE (UK)
6 Diamond Light Source Harwell Science and Innovation Campus Didcot Oxfordshire OX11 0DE (UK)
7 Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and
Molecular Engineering East China Normal University Shanghai 200062 (China)
8 The Chemical and Engineering Materials Division (CEMD) Neutron Sciences Directorate Oak Ridge
National Laboratory Oak Ridge TN 37831 (USA)
2
Contents
Supplementary Methods 4
Catalyst characterisation 4
DFT calculations and modelling of the INS spectra 5
Supplementary Notes 6
Interaction between GVL and NbAlH sites 6
Distribution of NbAlH sites 6
Inelastic neutron scattering 8
Supplementary Figures 9
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring) 9
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041) 10
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR 11
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD 12
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC 13
Fig S6 TGA and DSC plots of used catalysts after the conversion of pure GVL at 320 oC 14
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts 15
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after reaction 16
Fig S9 X-band EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at 77 K 17
Fig S10 XAS results of the fresh and used NbAlS-1(00270041) 18
Fig S11 27Al MAS NMR spectra of fresh and used zeolites 19
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD 20
Fig S13 X-band EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation at 77 K 21
Fig S14 Comparison of SXPD patterns of catalysts before and after adsorption of GVL 22
Fig S15 Comparison of the experimental data and Rietveld refinement for SXPD patterns 23
Fig S16 29Si NMR spectra of HZSM-5 and NbAlS-1 24
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated
INS spectra for 12 types of NbAlH sites 25
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination
of calculated INS spectra of different NbAlH sites 26
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection 27
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) 28
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 29
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment 30
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst 31
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC32
Supplementary Tables 33
3
Table S1 Textural properties and crystallite sizes of all zeolites used in this study 33
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra 34
Table S3 Summary of acidity of all zeolites used in this work 35
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers
produced from conversion of 30 GVL at 320 degC over catalysts 36
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in
aqueous solution (25-40 wt ) to butenes 37
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1 38
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption 39
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) 40
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) 42
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) 44
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) 46
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms from
the Rietveld refinements of the corresponding SXPD data at 25 degC 48
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio 49
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041) 50
Table S15 Assignment of INS peaks of bare NbAlS-1 51
Table S16 Assignment of INS peaks of GVL 52
Supplementary References 53
4
Supplementary Methods
Catalyst characterisation
Powder X-ray diffraction (PXRD) patterns were recorded on a Philips Xrsquopert X-ray diffractometer (40 kV
and 30 mA) using Cu Kα radiation (λ = 15406 Aring) N2 adsorption was carried out at 77 K on a Micromeritics
3Flex instrument after activating the samples for 10 h under dynamic vacuum at 423 K The crystal
morphology and size were measured by scanning electron microscopy (SEM) on a Quanta FEG 650
microscope The ratios of NbAlSi in the sample were quantified by EDX using multiple regions over a
sample on a Bruker XTrace instrument Thermogravimetric analysis was carried out with a SDTQ600 TA
instrument Samples were heated from room temperature to 800 degC at a rate of 5 degCmin under an air flow
Attenuated Total-Reflection Flourier Transformed Infrared (ATR-FTIR) spectra were collected with Nicolet
iS5 spectrometer Laser Raman spectra were obtained using a Horiba scientific XploRA PLUS Raman
microscope equipped with 1800 groovemm holographic gratings The samples were excited by the 532 nm
line of an Ar+ laser The acidity was measured by temperature-programmed desorption of ammonia (NH3-
TPD) with a Quantachrome Autosorb-1 equipped with a thermal conductivity detector (TCD) Typically 100
mg of sample was pre-treated in helium stream (30 mL minminus1) at 600 degC for 2 h The adsorption of NH3 was
carried out at 50 degC for 1 h The catalyst was flushed with helium at 100 degC for 2 h to remove physisorbed
NH3 from the catalyst surface The TPD profile was recorded at a heating rate of 10 degC min-1 from 100 degC to
600 degC The Broslashnsted and Lewis acid sites of the samples were investigated by FT-IR of adsorbed pyridine
in an in situ cell with CaF2 windows Wafers with a weight of 25 mg and radius of 65 mm were degassed for
1 h under vacuum at 600 degC Then pyridine was admitted and after equilibration the samples were
outgassed for 05 h at increasing temperatures (150 200 250 350 and 450 degC) The spectra were recorded
on a Nicolet iS50 FT-IR spectrometer Solid state 27Al NMR spectra were recorded with a frequency of
10424 MHz a spinning rate of 100 kHz and a recycling delay of 4 s Al(NO3)3 was used as the reference
for chemical shift Solid state 29Si NMR spectra were recorded with a frequency of 7946 MHz a spinning
rate of 100 kHz and a recycling delay of 10 s Tetramethylsilane was used as the reference for chemical
shift
For the EPR spectroscopy the sample was placed in a 28 mm od quartz tube and connected to a
vacuum line Prior to irradiation zeolite materials were activated by pumping at 10-5 Torr for 12 h at 150 ˚C
5
and then sealed under vacuum The samples were exposed to γ-irradiation from a 60Co source at 77 K to a
total dose of 44 MRad at a dose rate of 05 MRad h-1 CW EPR measurements were carried out at X-band
(97 GHz) using a commercial spectrometer Bruker EMX equipped with Oxford Instruments temperature
control system at 77 K EPR spectra were detected with modulation amplitudes of 02 and 1 mT and
microwave powers of ~5 mW were chosen to provide optimum signal intensity without saturation of spectral
lines Simulations of EPR spectra were performed using the EasySpin toolbox (Version 5220)1 for Matlab
DFT calculations and modelling of the INS spectra
Periodic density functional theory (periodic-DFT) calculations were carried out using the plane wave
pseudopotential method as implemented in the CASTEP code23 Exchange and correlation were
approximated using the Perdew-Burke-Ernzerhof (PBE) functional4 Ultra-soft pseudopotentials were
employed to account for the effects of core electrons Tkatchenko-Scheffler dispersion correction5 was used
for van der Waals interactions Energy cutoff for plane-wave basis was 380 eV Phonon frequencies were
obtained by diagonalisation of dynamical matrices computed using finite displacement method The atomic
displacements in each mode that are part of the CASTEP output enable visualization of the modes to aid
assignments and are also all that is required to generate the INS spectrum using the program OCLIMAX67
DFT calculations of the INS spectra for single GVL molecule and adsorbed GVL were carried out which
were used to identify the modes of vibrational features in the experimental INS spectra The calculated INS
spectrum shows the total transitions (up to 10 orders) In addition DFT calculations of the INS spectra for
bare NbAlS-1 were performed to investigate the distribution of NbAlH sites Due to the large number of
configurations involved in these simulations the CP2K code8 based on the mixed Gaussian and plane-wave
scheme9 and the Quickstep module10 were used The calculation used molecularly optimised Double-Zeta-
Valence plus Polarization (DZVP) basis set11 Goedecker-Teter-Hutter pseudopotentials12 and the PBE
exchange correlation functional4 The plane-wave energy cutoff was 400 Ry The DFT-D3 level correction
for dispersion interactions as implemented by Grimme et al13 was applied
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
1
Supplementary Information
Quantitative production of butenes from biomass-derived γ-valerolactone
catalysed by hetero-atomic MFI zeolite
Longfei Lin1 Alena M Sheveleva12 Ivan da Silva3 Christopher M A Parlett456 Zhimou Tang7 Yueming
Liu7 Mengtian Fan1 Xue Han1 Joseph H Carter1 Floriana Tuna1 Eric J L McInnes1 Yongqiang Cheng8
Luke L Daemen8 Svemir Rudić3 Anibal J Ramirez-Cuesta8 Chiu C Tang6 and Sihai Yang1
1 School of Chemistry and Photon Science Institute University of Manchester Manchester M13 9PL (UK)
2 International Tomography Center SB RAS and Novosibirsk State University Novosibirsk 630090
(Russia)
3 ISIS Facility STFC Rutherford Appleton Laboratory Chilton Oxfordshire OX11 0QX (UK)
4 School of Chemical Engineering and Analytical Science University of Manchester Manchester M13 9PL
(UK)
5 University of Manchester at Harwell Diamond Light Source Harwell Campus Didcot Oxfordshire
OX11 0DE (UK)
6 Diamond Light Source Harwell Science and Innovation Campus Didcot Oxfordshire OX11 0DE (UK)
7 Shanghai Key Laboratory of Green Chemistry and Chemical Processes School of Chemistry and
Molecular Engineering East China Normal University Shanghai 200062 (China)
8 The Chemical and Engineering Materials Division (CEMD) Neutron Sciences Directorate Oak Ridge
National Laboratory Oak Ridge TN 37831 (USA)
2
Contents
Supplementary Methods 4
Catalyst characterisation 4
DFT calculations and modelling of the INS spectra 5
Supplementary Notes 6
Interaction between GVL and NbAlH sites 6
Distribution of NbAlH sites 6
Inelastic neutron scattering 8
Supplementary Figures 9
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring) 9
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041) 10
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR 11
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD 12
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC 13
Fig S6 TGA and DSC plots of used catalysts after the conversion of pure GVL at 320 oC 14
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts 15
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after reaction 16
Fig S9 X-band EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at 77 K 17
Fig S10 XAS results of the fresh and used NbAlS-1(00270041) 18
Fig S11 27Al MAS NMR spectra of fresh and used zeolites 19
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD 20
Fig S13 X-band EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation at 77 K 21
Fig S14 Comparison of SXPD patterns of catalysts before and after adsorption of GVL 22
Fig S15 Comparison of the experimental data and Rietveld refinement for SXPD patterns 23
Fig S16 29Si NMR spectra of HZSM-5 and NbAlS-1 24
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated
INS spectra for 12 types of NbAlH sites 25
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination
of calculated INS spectra of different NbAlH sites 26
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection 27
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) 28
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 29
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment 30
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst 31
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC32
Supplementary Tables 33
3
Table S1 Textural properties and crystallite sizes of all zeolites used in this study 33
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra 34
Table S3 Summary of acidity of all zeolites used in this work 35
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers
produced from conversion of 30 GVL at 320 degC over catalysts 36
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in
aqueous solution (25-40 wt ) to butenes 37
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1 38
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption 39
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) 40
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) 42
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) 44
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) 46
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms from
the Rietveld refinements of the corresponding SXPD data at 25 degC 48
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio 49
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041) 50
Table S15 Assignment of INS peaks of bare NbAlS-1 51
Table S16 Assignment of INS peaks of GVL 52
Supplementary References 53
4
Supplementary Methods
Catalyst characterisation
Powder X-ray diffraction (PXRD) patterns were recorded on a Philips Xrsquopert X-ray diffractometer (40 kV
and 30 mA) using Cu Kα radiation (λ = 15406 Aring) N2 adsorption was carried out at 77 K on a Micromeritics
3Flex instrument after activating the samples for 10 h under dynamic vacuum at 423 K The crystal
morphology and size were measured by scanning electron microscopy (SEM) on a Quanta FEG 650
microscope The ratios of NbAlSi in the sample were quantified by EDX using multiple regions over a
sample on a Bruker XTrace instrument Thermogravimetric analysis was carried out with a SDTQ600 TA
instrument Samples were heated from room temperature to 800 degC at a rate of 5 degCmin under an air flow
Attenuated Total-Reflection Flourier Transformed Infrared (ATR-FTIR) spectra were collected with Nicolet
iS5 spectrometer Laser Raman spectra were obtained using a Horiba scientific XploRA PLUS Raman
microscope equipped with 1800 groovemm holographic gratings The samples were excited by the 532 nm
line of an Ar+ laser The acidity was measured by temperature-programmed desorption of ammonia (NH3-
TPD) with a Quantachrome Autosorb-1 equipped with a thermal conductivity detector (TCD) Typically 100
mg of sample was pre-treated in helium stream (30 mL minminus1) at 600 degC for 2 h The adsorption of NH3 was
carried out at 50 degC for 1 h The catalyst was flushed with helium at 100 degC for 2 h to remove physisorbed
NH3 from the catalyst surface The TPD profile was recorded at a heating rate of 10 degC min-1 from 100 degC to
600 degC The Broslashnsted and Lewis acid sites of the samples were investigated by FT-IR of adsorbed pyridine
in an in situ cell with CaF2 windows Wafers with a weight of 25 mg and radius of 65 mm were degassed for
1 h under vacuum at 600 degC Then pyridine was admitted and after equilibration the samples were
outgassed for 05 h at increasing temperatures (150 200 250 350 and 450 degC) The spectra were recorded
on a Nicolet iS50 FT-IR spectrometer Solid state 27Al NMR spectra were recorded with a frequency of
10424 MHz a spinning rate of 100 kHz and a recycling delay of 4 s Al(NO3)3 was used as the reference
for chemical shift Solid state 29Si NMR spectra were recorded with a frequency of 7946 MHz a spinning
rate of 100 kHz and a recycling delay of 10 s Tetramethylsilane was used as the reference for chemical
shift
For the EPR spectroscopy the sample was placed in a 28 mm od quartz tube and connected to a
vacuum line Prior to irradiation zeolite materials were activated by pumping at 10-5 Torr for 12 h at 150 ˚C
5
and then sealed under vacuum The samples were exposed to γ-irradiation from a 60Co source at 77 K to a
total dose of 44 MRad at a dose rate of 05 MRad h-1 CW EPR measurements were carried out at X-band
(97 GHz) using a commercial spectrometer Bruker EMX equipped with Oxford Instruments temperature
control system at 77 K EPR spectra were detected with modulation amplitudes of 02 and 1 mT and
microwave powers of ~5 mW were chosen to provide optimum signal intensity without saturation of spectral
lines Simulations of EPR spectra were performed using the EasySpin toolbox (Version 5220)1 for Matlab
DFT calculations and modelling of the INS spectra
Periodic density functional theory (periodic-DFT) calculations were carried out using the plane wave
pseudopotential method as implemented in the CASTEP code23 Exchange and correlation were
approximated using the Perdew-Burke-Ernzerhof (PBE) functional4 Ultra-soft pseudopotentials were
employed to account for the effects of core electrons Tkatchenko-Scheffler dispersion correction5 was used
for van der Waals interactions Energy cutoff for plane-wave basis was 380 eV Phonon frequencies were
obtained by diagonalisation of dynamical matrices computed using finite displacement method The atomic
displacements in each mode that are part of the CASTEP output enable visualization of the modes to aid
assignments and are also all that is required to generate the INS spectrum using the program OCLIMAX67
DFT calculations of the INS spectra for single GVL molecule and adsorbed GVL were carried out which
were used to identify the modes of vibrational features in the experimental INS spectra The calculated INS
spectrum shows the total transitions (up to 10 orders) In addition DFT calculations of the INS spectra for
bare NbAlS-1 were performed to investigate the distribution of NbAlH sites Due to the large number of
configurations involved in these simulations the CP2K code8 based on the mixed Gaussian and plane-wave
scheme9 and the Quickstep module10 were used The calculation used molecularly optimised Double-Zeta-
Valence plus Polarization (DZVP) basis set11 Goedecker-Teter-Hutter pseudopotentials12 and the PBE
exchange correlation functional4 The plane-wave energy cutoff was 400 Ry The DFT-D3 level correction
for dispersion interactions as implemented by Grimme et al13 was applied
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
2
Contents
Supplementary Methods 4
Catalyst characterisation 4
DFT calculations and modelling of the INS spectra 5
Supplementary Notes 6
Interaction between GVL and NbAlH sites 6
Distribution of NbAlH sites 6
Inelastic neutron scattering 8
Supplementary Figures 9
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring) 9
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041) 10
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR 11
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD 12
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC 13
Fig S6 TGA and DSC plots of used catalysts after the conversion of pure GVL at 320 oC 14
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts 15
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after reaction 16
Fig S9 X-band EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at 77 K 17
Fig S10 XAS results of the fresh and used NbAlS-1(00270041) 18
Fig S11 27Al MAS NMR spectra of fresh and used zeolites 19
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD 20
Fig S13 X-band EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation at 77 K 21
Fig S14 Comparison of SXPD patterns of catalysts before and after adsorption of GVL 22
Fig S15 Comparison of the experimental data and Rietveld refinement for SXPD patterns 23
Fig S16 29Si NMR spectra of HZSM-5 and NbAlS-1 24
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated
INS spectra for 12 types of NbAlH sites 25
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination
of calculated INS spectra of different NbAlH sites 26
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection 27
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) 28
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 29
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment 30
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst 31
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC32
Supplementary Tables 33
3
Table S1 Textural properties and crystallite sizes of all zeolites used in this study 33
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra 34
Table S3 Summary of acidity of all zeolites used in this work 35
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers
produced from conversion of 30 GVL at 320 degC over catalysts 36
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in
aqueous solution (25-40 wt ) to butenes 37
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1 38
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption 39
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) 40
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) 42
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) 44
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) 46
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms from
the Rietveld refinements of the corresponding SXPD data at 25 degC 48
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio 49
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041) 50
Table S15 Assignment of INS peaks of bare NbAlS-1 51
Table S16 Assignment of INS peaks of GVL 52
Supplementary References 53
4
Supplementary Methods
Catalyst characterisation
Powder X-ray diffraction (PXRD) patterns were recorded on a Philips Xrsquopert X-ray diffractometer (40 kV
and 30 mA) using Cu Kα radiation (λ = 15406 Aring) N2 adsorption was carried out at 77 K on a Micromeritics
3Flex instrument after activating the samples for 10 h under dynamic vacuum at 423 K The crystal
morphology and size were measured by scanning electron microscopy (SEM) on a Quanta FEG 650
microscope The ratios of NbAlSi in the sample were quantified by EDX using multiple regions over a
sample on a Bruker XTrace instrument Thermogravimetric analysis was carried out with a SDTQ600 TA
instrument Samples were heated from room temperature to 800 degC at a rate of 5 degCmin under an air flow
Attenuated Total-Reflection Flourier Transformed Infrared (ATR-FTIR) spectra were collected with Nicolet
iS5 spectrometer Laser Raman spectra were obtained using a Horiba scientific XploRA PLUS Raman
microscope equipped with 1800 groovemm holographic gratings The samples were excited by the 532 nm
line of an Ar+ laser The acidity was measured by temperature-programmed desorption of ammonia (NH3-
TPD) with a Quantachrome Autosorb-1 equipped with a thermal conductivity detector (TCD) Typically 100
mg of sample was pre-treated in helium stream (30 mL minminus1) at 600 degC for 2 h The adsorption of NH3 was
carried out at 50 degC for 1 h The catalyst was flushed with helium at 100 degC for 2 h to remove physisorbed
NH3 from the catalyst surface The TPD profile was recorded at a heating rate of 10 degC min-1 from 100 degC to
600 degC The Broslashnsted and Lewis acid sites of the samples were investigated by FT-IR of adsorbed pyridine
in an in situ cell with CaF2 windows Wafers with a weight of 25 mg and radius of 65 mm were degassed for
1 h under vacuum at 600 degC Then pyridine was admitted and after equilibration the samples were
outgassed for 05 h at increasing temperatures (150 200 250 350 and 450 degC) The spectra were recorded
on a Nicolet iS50 FT-IR spectrometer Solid state 27Al NMR spectra were recorded with a frequency of
10424 MHz a spinning rate of 100 kHz and a recycling delay of 4 s Al(NO3)3 was used as the reference
for chemical shift Solid state 29Si NMR spectra were recorded with a frequency of 7946 MHz a spinning
rate of 100 kHz and a recycling delay of 10 s Tetramethylsilane was used as the reference for chemical
shift
For the EPR spectroscopy the sample was placed in a 28 mm od quartz tube and connected to a
vacuum line Prior to irradiation zeolite materials were activated by pumping at 10-5 Torr for 12 h at 150 ˚C
5
and then sealed under vacuum The samples were exposed to γ-irradiation from a 60Co source at 77 K to a
total dose of 44 MRad at a dose rate of 05 MRad h-1 CW EPR measurements were carried out at X-band
(97 GHz) using a commercial spectrometer Bruker EMX equipped with Oxford Instruments temperature
control system at 77 K EPR spectra were detected with modulation amplitudes of 02 and 1 mT and
microwave powers of ~5 mW were chosen to provide optimum signal intensity without saturation of spectral
lines Simulations of EPR spectra were performed using the EasySpin toolbox (Version 5220)1 for Matlab
DFT calculations and modelling of the INS spectra
Periodic density functional theory (periodic-DFT) calculations were carried out using the plane wave
pseudopotential method as implemented in the CASTEP code23 Exchange and correlation were
approximated using the Perdew-Burke-Ernzerhof (PBE) functional4 Ultra-soft pseudopotentials were
employed to account for the effects of core electrons Tkatchenko-Scheffler dispersion correction5 was used
for van der Waals interactions Energy cutoff for plane-wave basis was 380 eV Phonon frequencies were
obtained by diagonalisation of dynamical matrices computed using finite displacement method The atomic
displacements in each mode that are part of the CASTEP output enable visualization of the modes to aid
assignments and are also all that is required to generate the INS spectrum using the program OCLIMAX67
DFT calculations of the INS spectra for single GVL molecule and adsorbed GVL were carried out which
were used to identify the modes of vibrational features in the experimental INS spectra The calculated INS
spectrum shows the total transitions (up to 10 orders) In addition DFT calculations of the INS spectra for
bare NbAlS-1 were performed to investigate the distribution of NbAlH sites Due to the large number of
configurations involved in these simulations the CP2K code8 based on the mixed Gaussian and plane-wave
scheme9 and the Quickstep module10 were used The calculation used molecularly optimised Double-Zeta-
Valence plus Polarization (DZVP) basis set11 Goedecker-Teter-Hutter pseudopotentials12 and the PBE
exchange correlation functional4 The plane-wave energy cutoff was 400 Ry The DFT-D3 level correction
for dispersion interactions as implemented by Grimme et al13 was applied
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
3
Table S1 Textural properties and crystallite sizes of all zeolites used in this study 33
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra 34
Table S3 Summary of acidity of all zeolites used in this work 35
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers
produced from conversion of 30 GVL at 320 degC over catalysts 36
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in
aqueous solution (25-40 wt ) to butenes 37
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1 38
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption 39
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) 40
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) 42
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) 44
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) 46
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms from
the Rietveld refinements of the corresponding SXPD data at 25 degC 48
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio 49
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041) 50
Table S15 Assignment of INS peaks of bare NbAlS-1 51
Table S16 Assignment of INS peaks of GVL 52
Supplementary References 53
4
Supplementary Methods
Catalyst characterisation
Powder X-ray diffraction (PXRD) patterns were recorded on a Philips Xrsquopert X-ray diffractometer (40 kV
and 30 mA) using Cu Kα radiation (λ = 15406 Aring) N2 adsorption was carried out at 77 K on a Micromeritics
3Flex instrument after activating the samples for 10 h under dynamic vacuum at 423 K The crystal
morphology and size were measured by scanning electron microscopy (SEM) on a Quanta FEG 650
microscope The ratios of NbAlSi in the sample were quantified by EDX using multiple regions over a
sample on a Bruker XTrace instrument Thermogravimetric analysis was carried out with a SDTQ600 TA
instrument Samples were heated from room temperature to 800 degC at a rate of 5 degCmin under an air flow
Attenuated Total-Reflection Flourier Transformed Infrared (ATR-FTIR) spectra were collected with Nicolet
iS5 spectrometer Laser Raman spectra were obtained using a Horiba scientific XploRA PLUS Raman
microscope equipped with 1800 groovemm holographic gratings The samples were excited by the 532 nm
line of an Ar+ laser The acidity was measured by temperature-programmed desorption of ammonia (NH3-
TPD) with a Quantachrome Autosorb-1 equipped with a thermal conductivity detector (TCD) Typically 100
mg of sample was pre-treated in helium stream (30 mL minminus1) at 600 degC for 2 h The adsorption of NH3 was
carried out at 50 degC for 1 h The catalyst was flushed with helium at 100 degC for 2 h to remove physisorbed
NH3 from the catalyst surface The TPD profile was recorded at a heating rate of 10 degC min-1 from 100 degC to
600 degC The Broslashnsted and Lewis acid sites of the samples were investigated by FT-IR of adsorbed pyridine
in an in situ cell with CaF2 windows Wafers with a weight of 25 mg and radius of 65 mm were degassed for
1 h under vacuum at 600 degC Then pyridine was admitted and after equilibration the samples were
outgassed for 05 h at increasing temperatures (150 200 250 350 and 450 degC) The spectra were recorded
on a Nicolet iS50 FT-IR spectrometer Solid state 27Al NMR spectra were recorded with a frequency of
10424 MHz a spinning rate of 100 kHz and a recycling delay of 4 s Al(NO3)3 was used as the reference
for chemical shift Solid state 29Si NMR spectra were recorded with a frequency of 7946 MHz a spinning
rate of 100 kHz and a recycling delay of 10 s Tetramethylsilane was used as the reference for chemical
shift
For the EPR spectroscopy the sample was placed in a 28 mm od quartz tube and connected to a
vacuum line Prior to irradiation zeolite materials were activated by pumping at 10-5 Torr for 12 h at 150 ˚C
5
and then sealed under vacuum The samples were exposed to γ-irradiation from a 60Co source at 77 K to a
total dose of 44 MRad at a dose rate of 05 MRad h-1 CW EPR measurements were carried out at X-band
(97 GHz) using a commercial spectrometer Bruker EMX equipped with Oxford Instruments temperature
control system at 77 K EPR spectra were detected with modulation amplitudes of 02 and 1 mT and
microwave powers of ~5 mW were chosen to provide optimum signal intensity without saturation of spectral
lines Simulations of EPR spectra were performed using the EasySpin toolbox (Version 5220)1 for Matlab
DFT calculations and modelling of the INS spectra
Periodic density functional theory (periodic-DFT) calculations were carried out using the plane wave
pseudopotential method as implemented in the CASTEP code23 Exchange and correlation were
approximated using the Perdew-Burke-Ernzerhof (PBE) functional4 Ultra-soft pseudopotentials were
employed to account for the effects of core electrons Tkatchenko-Scheffler dispersion correction5 was used
for van der Waals interactions Energy cutoff for plane-wave basis was 380 eV Phonon frequencies were
obtained by diagonalisation of dynamical matrices computed using finite displacement method The atomic
displacements in each mode that are part of the CASTEP output enable visualization of the modes to aid
assignments and are also all that is required to generate the INS spectrum using the program OCLIMAX67
DFT calculations of the INS spectra for single GVL molecule and adsorbed GVL were carried out which
were used to identify the modes of vibrational features in the experimental INS spectra The calculated INS
spectrum shows the total transitions (up to 10 orders) In addition DFT calculations of the INS spectra for
bare NbAlS-1 were performed to investigate the distribution of NbAlH sites Due to the large number of
configurations involved in these simulations the CP2K code8 based on the mixed Gaussian and plane-wave
scheme9 and the Quickstep module10 were used The calculation used molecularly optimised Double-Zeta-
Valence plus Polarization (DZVP) basis set11 Goedecker-Teter-Hutter pseudopotentials12 and the PBE
exchange correlation functional4 The plane-wave energy cutoff was 400 Ry The DFT-D3 level correction
for dispersion interactions as implemented by Grimme et al13 was applied
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
4
Supplementary Methods
Catalyst characterisation
Powder X-ray diffraction (PXRD) patterns were recorded on a Philips Xrsquopert X-ray diffractometer (40 kV
and 30 mA) using Cu Kα radiation (λ = 15406 Aring) N2 adsorption was carried out at 77 K on a Micromeritics
3Flex instrument after activating the samples for 10 h under dynamic vacuum at 423 K The crystal
morphology and size were measured by scanning electron microscopy (SEM) on a Quanta FEG 650
microscope The ratios of NbAlSi in the sample were quantified by EDX using multiple regions over a
sample on a Bruker XTrace instrument Thermogravimetric analysis was carried out with a SDTQ600 TA
instrument Samples were heated from room temperature to 800 degC at a rate of 5 degCmin under an air flow
Attenuated Total-Reflection Flourier Transformed Infrared (ATR-FTIR) spectra were collected with Nicolet
iS5 spectrometer Laser Raman spectra were obtained using a Horiba scientific XploRA PLUS Raman
microscope equipped with 1800 groovemm holographic gratings The samples were excited by the 532 nm
line of an Ar+ laser The acidity was measured by temperature-programmed desorption of ammonia (NH3-
TPD) with a Quantachrome Autosorb-1 equipped with a thermal conductivity detector (TCD) Typically 100
mg of sample was pre-treated in helium stream (30 mL minminus1) at 600 degC for 2 h The adsorption of NH3 was
carried out at 50 degC for 1 h The catalyst was flushed with helium at 100 degC for 2 h to remove physisorbed
NH3 from the catalyst surface The TPD profile was recorded at a heating rate of 10 degC min-1 from 100 degC to
600 degC The Broslashnsted and Lewis acid sites of the samples were investigated by FT-IR of adsorbed pyridine
in an in situ cell with CaF2 windows Wafers with a weight of 25 mg and radius of 65 mm were degassed for
1 h under vacuum at 600 degC Then pyridine was admitted and after equilibration the samples were
outgassed for 05 h at increasing temperatures (150 200 250 350 and 450 degC) The spectra were recorded
on a Nicolet iS50 FT-IR spectrometer Solid state 27Al NMR spectra were recorded with a frequency of
10424 MHz a spinning rate of 100 kHz and a recycling delay of 4 s Al(NO3)3 was used as the reference
for chemical shift Solid state 29Si NMR spectra were recorded with a frequency of 7946 MHz a spinning
rate of 100 kHz and a recycling delay of 10 s Tetramethylsilane was used as the reference for chemical
shift
For the EPR spectroscopy the sample was placed in a 28 mm od quartz tube and connected to a
vacuum line Prior to irradiation zeolite materials were activated by pumping at 10-5 Torr for 12 h at 150 ˚C
5
and then sealed under vacuum The samples were exposed to γ-irradiation from a 60Co source at 77 K to a
total dose of 44 MRad at a dose rate of 05 MRad h-1 CW EPR measurements were carried out at X-band
(97 GHz) using a commercial spectrometer Bruker EMX equipped with Oxford Instruments temperature
control system at 77 K EPR spectra were detected with modulation amplitudes of 02 and 1 mT and
microwave powers of ~5 mW were chosen to provide optimum signal intensity without saturation of spectral
lines Simulations of EPR spectra were performed using the EasySpin toolbox (Version 5220)1 for Matlab
DFT calculations and modelling of the INS spectra
Periodic density functional theory (periodic-DFT) calculations were carried out using the plane wave
pseudopotential method as implemented in the CASTEP code23 Exchange and correlation were
approximated using the Perdew-Burke-Ernzerhof (PBE) functional4 Ultra-soft pseudopotentials were
employed to account for the effects of core electrons Tkatchenko-Scheffler dispersion correction5 was used
for van der Waals interactions Energy cutoff for plane-wave basis was 380 eV Phonon frequencies were
obtained by diagonalisation of dynamical matrices computed using finite displacement method The atomic
displacements in each mode that are part of the CASTEP output enable visualization of the modes to aid
assignments and are also all that is required to generate the INS spectrum using the program OCLIMAX67
DFT calculations of the INS spectra for single GVL molecule and adsorbed GVL were carried out which
were used to identify the modes of vibrational features in the experimental INS spectra The calculated INS
spectrum shows the total transitions (up to 10 orders) In addition DFT calculations of the INS spectra for
bare NbAlS-1 were performed to investigate the distribution of NbAlH sites Due to the large number of
configurations involved in these simulations the CP2K code8 based on the mixed Gaussian and plane-wave
scheme9 and the Quickstep module10 were used The calculation used molecularly optimised Double-Zeta-
Valence plus Polarization (DZVP) basis set11 Goedecker-Teter-Hutter pseudopotentials12 and the PBE
exchange correlation functional4 The plane-wave energy cutoff was 400 Ry The DFT-D3 level correction
for dispersion interactions as implemented by Grimme et al13 was applied
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
5
and then sealed under vacuum The samples were exposed to γ-irradiation from a 60Co source at 77 K to a
total dose of 44 MRad at a dose rate of 05 MRad h-1 CW EPR measurements were carried out at X-band
(97 GHz) using a commercial spectrometer Bruker EMX equipped with Oxford Instruments temperature
control system at 77 K EPR spectra were detected with modulation amplitudes of 02 and 1 mT and
microwave powers of ~5 mW were chosen to provide optimum signal intensity without saturation of spectral
lines Simulations of EPR spectra were performed using the EasySpin toolbox (Version 5220)1 for Matlab
DFT calculations and modelling of the INS spectra
Periodic density functional theory (periodic-DFT) calculations were carried out using the plane wave
pseudopotential method as implemented in the CASTEP code23 Exchange and correlation were
approximated using the Perdew-Burke-Ernzerhof (PBE) functional4 Ultra-soft pseudopotentials were
employed to account for the effects of core electrons Tkatchenko-Scheffler dispersion correction5 was used
for van der Waals interactions Energy cutoff for plane-wave basis was 380 eV Phonon frequencies were
obtained by diagonalisation of dynamical matrices computed using finite displacement method The atomic
displacements in each mode that are part of the CASTEP output enable visualization of the modes to aid
assignments and are also all that is required to generate the INS spectrum using the program OCLIMAX67
DFT calculations of the INS spectra for single GVL molecule and adsorbed GVL were carried out which
were used to identify the modes of vibrational features in the experimental INS spectra The calculated INS
spectrum shows the total transitions (up to 10 orders) In addition DFT calculations of the INS spectra for
bare NbAlS-1 were performed to investigate the distribution of NbAlH sites Due to the large number of
configurations involved in these simulations the CP2K code8 based on the mixed Gaussian and plane-wave
scheme9 and the Quickstep module10 were used The calculation used molecularly optimised Double-Zeta-
Valence plus Polarization (DZVP) basis set11 Goedecker-Teter-Hutter pseudopotentials12 and the PBE
exchange correlation functional4 The plane-wave energy cutoff was 400 Ry The DFT-D3 level correction
for dispersion interactions as implemented by Grimme et al13 was applied
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
6
Supplementary Notes
Interaction between GVL and NbAlH sites
Synchrotron XPD has been successfully applied to study the interaction between guest molecules
and porous materials such as binding of hydrocarbons in porous metal-organic frameworks14 binding of
GVL in ZnZSM-515 and binding of pyridine in HZSM-516 In this study over 3100 hkl reflections were used
for the structural refinement which allowed for extensive structural variables to be refined in a satisfactory
manner It is almost impossible to distinguish between Al and Si (Z=13 and 14 respectively) sites using X-
rays diffraction Although Nb (Z=41) is heavier the low occupancy of Nb precludes the determination of its
precise location in the framework Recently the distribution of active sites in H-ZSM-516 and in ZnZSM-515
has been successfully determined by examining the intermolecular distances and angles between guest
molecules and framework sites For example protonic acid sites of H-ZSM-5 have been located by
examining the atomic distances and angles between pyridines and framework atoms16 GVL can be adsorbed
on Broslashnsted acid sites upon protonation of the C=O group17 while the O in the ring of GVL can be adsorbed
on Nb(V) sites18 Thus the distribution of active sites in NbAlS-1 has been revealed by a detailed
examination of the GVL-NbAlS-1 binding distances particularly that between O1GVL and T sites and
between O2GVL and Ozeolites (see Supplementary Table 12) Importantly the distances between O1GVLI and T8
and between O1GVLII and T6 are shortest in both GVL-adsorbed NbAlS-1 and NbS-1 indicating that Nb sites
are likely located at T8 and T6 positions Similarly the distances between O2GVLI and O25zeolites and that
between O2GVLII and O26zeolite are shortest in both GVL-adsorbed NbAlS-1 and HZSM-5 suggesting that
protonic acid sites are likely located at O25-T9 and O26-T10 centres In addition XAS measurements (Fig
3b) suggest that the Nb pre-edge position is influenced with an apparent blue-shift (~08 eV) for NbAlS-1
upon adsorption of GVL while no such shift is witnessed for NbS-1 This observation reflects the preferred
adsorption geometry within the bifunctional (Al and Nb-containing) zeolite NbAlS-1 consistent with the
crystallographic study
Distribution of NbAlH sites
The 29Si NMR spectra of NbAlS-1(00270041) and HZM-5(0041) show notable difference in the range of
-110 to -90 ppm (Supplementary Fig 16a) Curves are de-convoluted by Guassian and Lorentzian line
shapes The assignments and integration of peak areas are listed in Supplementary Table 13 The (Al+Si)Si
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
7
ratios calculated from the 29Si NMR data are highly consistent with that obtained from EDX The peak at -98
ppm is absent in the spectrum of HZSM-5(0041) indicating the absence of Si(OSi)2(OAl)2 species
(Supplementary Fig 16b) consistent with previous reports1920 By contrast the peak at -98 ppm is observed
in the NMR spectrum of NbAlS-1(00270041) suggesting the presence of Si(OSi)2(OAl)(ONb) species
(Supplementary Fig 16c and Supplementary Table 13)
Recently the distribution of protons in LTA zeolite has been studied using periodic DFT calculations
and INS2122 The distribution of NbAlH sites in NbAlS-1(00270041) has been further investigated by
combining INS and DFT calculations Four types of possible species ie species I [NbOSiOAl] species II
[NbOSiOSiOAl] species III [NbO(SiO)nAl (n ge 3)] and species IV (isolated Al no Nb around) and twelve
types of NbAlH species in NbAlS-1 have been simulated (Supplementary Table 14) From the synchrotron
XPD and Rietveld Refinement species I and II present in NbAlS-1(00270041) (Fig 4f and 4i) and thus
Nb and Al are positioned at T8 and T9 respectively for species I and at T6 and T10 respectively for
species II for the calculation of corresponding INS spectra The H sites have the same probability to appear
near all four O around Al and are thus attached to O25 O8 O18 O9 O26 O15 O10 and O9 respectively
(NbAlH_1-8 Supplementary Table 14) In species III Nb and Al are not adjacent Nb is positioned at T8 or
T6 and Al is moved to T12 (NbAlH_9) or T7 (NbAlH_10) Since the NbAl ratio is 0027004 325 of
Al are isolated (species IV) The isolated Al is positioned at T2 (NbAlH_11) or T4 (NbAlH_12) All
twelve NbAlH sites are simulated independently by DFT and the calculated INS spectra are compared with
the experimental data of bare NbAlS-1(00270041) (Supplementary Fig 17) As there is an uncertainty on
the position of H the calculated INS spectra are given different weights to assemble the combined spectrum
for NbAlS-1(00270041) Species I and II have the same occupancy (determined by Rietveld Refinement)
and they were given the same weight Based upon the NbAl ratio and 29Si NMR results the weights of all
four species are calculated (Supplementary Table 14) The spectrum of combination 1 is produced by
combining twelve spectra with calculated weights All peaks in combination 1 fit with those in the
experimental data particularly the peaks assigned to -OH in-plane bending and Si-O stretching at 1086 and
1191 cm-1 respectively (Supplementary Fig 18 and Supplementary Table 15) The intensities of peaks at
245-534 cm-1 (assigned to relaxation of zeolite framework and -OH out-of-plane bending in combination 1)
are lower than that of the experimental data because only one unit cell and a simplified model were used and
external SiOH groups are not considered in the simulation Combination 2 is produced without species I and
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
8
II (Supplementary Fig 18) and a number of peaks (77 157 237 and 317 cm-1) are absent compared with the
experimental data demonstrating the presence of species I and II that promotes the adsorption of GVL in
NbAlS-1 via the ldquochelatingrdquo mechanism
Inelastic neutron scattering
Direct visualisation of the interaction between adsorbed GVL and the active sites is crucial to understand the
molecular details of adsorption activation and ring-open and decarboxylation of GVL into butenes INS is a
powerful neutron spectroscopy technique to investigate the dynamics (particularly for the deformational and
conformational modes) of GVL It has several advantages
INS spectroscopy is sensitive to the vibrations of hydrogen atoms and hydrogen is ten times more
visible than other elements due to its high neutron cross-section
The technique is not subject to any optical selection rules All vibrations are active and in principle
measurable
INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case for
optical techniques
INS spectra can be readily and accurately modelled the intensities are proportional to the concentration
of elements in the sample and their cross-sections and the measured INS intensities relate
straightforwardly to the associated displacements of the scattering atom Treatment of background
correction is also straightforward
Neutrons penetrate deeply into materials and pass readily through the walls of metal containers making
neutrons ideal to measure bulk properties of this material (in this case for 11 g catalyst)
INS spectrometers cover the whole range of the molecular vibrational spectrum 0-500 meV (0-4000 cm-
1)
INS data can be collected at low temperature (lt 15 K in this case) where the thermal motion of the
catalyst the adsorbed GVL and the reacted intermediate molecules can be significantly reduced
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
9
Supplementary Figures
Fig S1 Comparison of PXRD patterns of HZSM-5 NbS-1 and NbAlS-1 (λ = 15406 Aring)
5 10 15 20 25 30 35 40
NbAlS-1(00270041)
NbAlS-1(00400271)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
In
tensity (
au
)
2 (degree)
HZSM-5(00271)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
10
Fig S2 SEM images of (a) HZSM-5(0041) (b) NbS-1 (00271) and (c) NbAlS-1(00270041)
a
500 nm
b
500 nm
c
500 nm
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
11
Fig S3 Characterisation of the acidity of zeolites by Pyridine-IR (a) Py-IR spectra after vacuum treatment
at 150 oC Py-IR spectra of (b) HZSM-5(0041) (c) NbS-1(00271) and (d) NbAlS-1(00270041) after
vacuum treatment at variable temperatures The peaks at 1454 and 1545 cm-1 are assigned to the
coordinatively bound pyridine molecules on Lewis acid sites and pyridinium ion on Broslashnsted acid sites
respectively23 Both the coordinatively bound pyridine and pyridinium ion have the vibration peak at 1490
cm-1 23 The Lewis acid band is centred at 1454 cm-1 in the spectra of HZSM-5 while it shifts to 1447 cm-1 in
the spectra of Nb-doped zeolite which is similar to the reported Lewis acid band (centred at 1448 cm-1) in
niobium phosphate24 The decrease of frequency of the band is related to the reduced stability of the pyridine
complex23 which is verified by the desorption experiments b c and d show the Py-IR spectra of HZSM-
5(0041) NbS-1(00271) and NbAlS-1 (00270041) respectively after desorption of pyridine at variable
temperatures With the increase of temperature the peak intensities related to both Lewis and Broslashnsted acid
sites of HZSM-5 decrease slowly Both peaks are visible even after the vacuum treatment at 450 degC (b)
However the intensities of peaks at 1447 cm-1 in the spectra of NbS-1 and NbAlS-1 decreased dramatically
upon increasing temperature and disappeared at 350 degC (c and d) Also the peaks related to Broslashnsted acid
sites on NbAlS-1 samples disappeared even at 250 degC (c and d) This result indicates that the NbAlS-1
samples have only weak Lewis and weak Broslashnsted acid sites entirely consistent with the NH3-TPD results in
Supplementary Fig 4
a b
cd
1420 1440 1460 1480 1500 1520 1540 1560 1580
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5 (00271)
Inte
nsity (
au
)
Wavenumber (cm-1)
1420 1440 1460 1480 1500 1520 1540 1560 1580
Ine
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
1420 1440 1460 1480 1500 1520 1540 1560 1580
Inte
nsity (
au
)
Wavenumber (cm-1)
150 oC
200 oC
250 oC
350 oC
450 oC
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
12
Fig S4 Characterisation of the acidity of zeolites by NH3-TPD Two peaks at 240 and 435 degC correspond to
NH3 eluted from the weak and strong acid sites respectively25
100 150 200 250 300 350 400 450 500 550 600
Inte
nsity (
au
)
Temperature (oC)
NbAlS-1(00400271)
NbAlS-1(00270041)
NbS-1(0041)
NbS-1(00271)
HZSM-5(00671)
HZSM-5(0041)
HZSM-5(00271)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
13
Fig S5 GC-MS results of the products from the conversion of GVL at 320 oC (a) Gas and (b) liquid
products from conversion of pure GVL over HZSM-5(0041) (c) Gas and (d) liquid products from
conversion of pure GVL over NbS-1(00271) (e) Gas and (f) liquid products from conversion of pure GVL
over NbAlS-1(00270041) (g) Gas and (h) liquid products from conversion of 30 GVL over NbAlS-
1(00270041) The water in g is solely from the feeding solution rather than produced from dehydration as
no dehydration products are observed
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
b
d
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
a
c
N2
CO2
C2H4 C2H6 C3H6 C3H8
C4H10
C4H8
H2O
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2
C4H8
H2O
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
fe
Pentenoic
acid isomers
Pentenoic
acid isomers
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
Aromatics
Pentenoic
acid isomers
g h
4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
N2
CO2C4H8
N2
CO2
C4H8
H2O
C2H4 C2H6 C3H6
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
0 1 2 3 4 5 6 7 8 9 10
Inte
nsity (
au
)
Retention time (min)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
14
Fig S6 TGA (black) and DSC (red) plots of used HZSM-5(0041) (a) and NbAlS-1(00270041) (b)
catalysts after the conversion of pure GVL at 320 oC The by-products (eg coke) deposited on the surface
of used HZSM-5(0041) are significantly more stable than those on used NbAlS-1(00270041)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
500
Hea
t flow
(W
g)
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
-10
-08
-06
-04
-02
00
02
04
06
08
10
430
He
at flow
(W
g)
330
a b
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
15
Fig S7 TGA plots of used NbAlS-1(00270041) catalysts after the conversion of pure GVL (black) and 30
wt GVL (red) at 320 oC The presence of water in this catalytic system effectively hindered the formation
of by-products on the catalyst surface
100 200 300 400 500 600 700 800
86
88
90
92
94
96
98
100
Weig
ht (
)
Temperature (oC)
for 30 GVL feeding
for pure GVL feeding
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
16
Fig S8 Comparison of FTIR spectra of NbAlS-1 before and after the conversion of 30wt GVL at 320 oC
for 180 h
1400 1300 1200 1100 1000 900 800 700 600
Absorb
ance (
au
)
Wavenumber (cm-1)
NbAlS-1(00270041) used
NbAlS-1(00270041)
971
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
17
Fig S9 X-band (ca 9 GHz) EPR spectra of NbAlS-1 and post-reaction zeolites activated by γ-irradiation at
77 K (a) wide magnetic field-sweep highlighting the induced Nb(IV) signals in NbAlS-1(00270041) and
the used sample and (b) narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-
Si signals in fresh and used NbAlS-1(00270041) samples
a
b
100 150 200 250 300 350 400 450 500 550
Nb simulation
NbAlS-1(00270041)
used
Inte
nsity (
au
)
NbAlS-1(00270041)
Magnetic field (mT)
300 310 320 330 340 350 360
NbAlS-1(00270041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
NbAlS-1(00270041)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
18
Fig S10 (a) XAS spectra of the fresh and used NbAlS-1(00270041) (b) Phase-corrected k3-weighted
Fourier Transform of the EXAFS spectra for fresh and used NbAlS-1(00270041) The stability of the Nb
active sites within NbAlS-1(00270041) was verified by Nb K edge XAS with both fresh and used
catalysts exhibiting the same pre-edge XANES and EXAFS features
00
04
08
12
16
20
18800 19075 19350 19625 19900
No
rm a
bso
rptio
n (
au
)
Energy (eV)
NbAlS-1(00270041)
0
1
2
3
4
5
6
7
0 2 4 6
χ(R
)(Aring
-4)
Radial distance (Aring)
a b
NbAlS-1(00270041)
NbAlS-1(00270041) used
NbAlS-1(00270041)
used
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
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and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
19
Fig S11 27Al MAS NMR spectra of fresh and used zeolites Chemical shifts at 0 and 55 ppm are assigned to
six-coordinate extra-framework and four-coordinate framework aluminum species respectively26
100 80 60 40 20 0 -20 -40
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
27Al chemical shift (ppm)
HZSM-5(0041)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
20
Fig S12 Characterisation of the acidity of fresh and used zeolites by NH3-TPD
100 150 200 250 300 350 400 450 500 550 600
In
tensity (
au
)
Temperature (oC)
NbAlS-1(00270041) used
NbAlS-1(00270041)
HZSM-5(0041) used
HZSM-5(0041)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
21
Fig S13 X-band (ca 9 GHz) EPR spectra of HZSM-5 and post-reaction zeolites activated by γ-irradiation
at 77 K narrow magnetic field-sweep highlighting the induced electron hole defect Al-O-Si signals in
HZSM-5 (0041) and the used sample
300 310 320 330 340 350 360
HZSM-50041) used
Al simulation
Inte
nsity (
au
)
Magnetic field (mT)
HZSM-5(0041)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
22
Fig S14 Comparison of SXPD patterns of (a) HZSM-5(0041) (b) NbS-1(00271) and (c) NbAlS-
1(00270041) before and after adsorption of GVL at room temperature [λ = 082487(1) Aring]
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbAlS-1(0027041)
GVLNbAlS-1(0027041)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
NbS-1(00271)
GVLNbS-1(00271)
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
HZSM-5(0041)
GVLHZSM-5(0041)
a
b
c
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
23
Fig S15 Comparison of the experimental data (black line) and Rietveld refinement (red line) and the
difference between them (grey line) for SXPD patterns of (ab) GVLHZSM-5(0041) (cd) GVLNbS-
1(00271) (ef) GVLNbAlS-1(00270041) at room temperature at a 2θ range of (ace) 3 - 20deg and
(bdf) 20 - 50deg [λ = 082487(1) Aring]
a b
c d
e f
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbS-1(00271) obs
GVLNbS-1(00271) cal
GVLNbS-1(00271) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLHZSM-5(0041) obs
GVLHZSM-5(0041) cal
GVLHZSM-5(0041) diff
4 6 8 10 12 14 16 18 20
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
20 25 30 35 40 45 50
Inte
nsity (
au
)
2 (degree)
GVLNbAlS-1(00270041) obs
GVLNbAlS-1(00270041) cal
GVLNbAlS-1(00270041) diff
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
24
Fig S16 (a) 29Si NMR spectra of HZSM-5 and NbAlS-1 de-convolution of 29Si NMR spectra of HZSM-5
(b) and NbAlS-1 (c) by Guassian and Lorentzian line shapes
a
b
c
-125 -120 -115 -110 -105 -100 -95 -90 -85
-1023
-1076
-1138
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-4
Cumulative Fitted Peak
-1171
-125 -120 -115 -110 -105 -100 -95 -90 -85
-924-983
-1026
-1057
-1124
29Si chemical shift (ppm)
Experimental Spectrum
Fitted Peak 1-6
Cumulative Fitted Peak
-1162
-125 -120 -115 -110 -105 -100 -95 -90 -8529
Si chemical shift (ppm)
NbAlS-1(00270041)
HZSM-5(0041)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
25
Fig S17 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and calculated INS
spectra for 12 types of NbAlH sites
0 200 400 600 800 1000 1200 1400 1600
1211109876
4
23
5
1
Bare NbAlS-1 (exp)
S(Q
) (a
u)
Neutron energy loss (cm-1)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
26
Fig S18 Comparison of the experimental INS spectrum of bare NbAlS-1(00270041) and combination of
calculated INS spectra of different NbAlH sites Combination 1 = 3125Site I + 3125Site II +
5Site III + 325Site IV Combination 2 = 675Site III + 325Site IV Site I = 025(NbAlH_1 +
NbAlH_2 + NbAlH_3 + NbAlH_4) Site II = 025(NbAlH_5 + NbAlH_6 + NbAlH_7 +
NbAlH_8) Site III = 05(NbAlH_9 + NbAlH_10) Site IV = 05(NbAlH_11 + NbAlH_12)
Abscissa is scaled down by 097 for combination 1 and 2
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Bare NbAlS-1 (exp)
Combination 1
Combination 2
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
27
Fig S19 Schematic view of the procedure of in situ INS experiment and data collection
Zeolite (Calcined)
Zeolite (activated)
Heating at 450 oC under
He flow for 3 h
Zeolite (Adsorbed)
INS collection 1
Zeolite (Reaction at 280 C)
Adsorption of GVL at 135 oC
Zeolite (Reaction at 300 C)
Zeolite (Reaction at 320 C)
Reaction at 280 oC for 3 min
Reaction at 300 oC for 3 min
Reaction at 320 oC for 3 min
INS collection 2
INS collection 3
INS collection 4
INS collection 5
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
28
Fig S20 Comparison of the experimental INS spectra of condensed GVL in the solid state (black) and
calculated INS spectra of single GVL molecule (red) The crystal structure of solid GVL is unavailable in the
database
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental GVL
Calculated GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
29
Fig S21 Comparison of the experimental and calculated INS spectra of adsorbed GVL molecules on
NbAlS-1 The structure model derived from SXPD experiments was used for initial DFT modelling where
the positional disorder has been removed in the calculation and this partially accounts for the discrepancies
observed between calculated and experimental INS plots
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Experimental adsorbed GVL
Calculated adsorbed GVL
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
30
Fig S22 View of the INS spectrum for the empty catalysis cell used for this experiment The empty can has
the features below 300 cm-1 and at approximately 457 and 659 cm-1
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Empty can
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
31
Fig S23 Comparison of the experimental INS spectra for bare and GVL-adsorbed catalyst Spectra shown
are after subtraction of the empty cell The INS spectrum of the catalyst on GVL adsorption at 135 degC shows
a significant increase in total intensity demonstrating the binding of GVL to the catalyst sites
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
GVLNbAlS-1(00270041)
Bare NbAlS-1(00270041)
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
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and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
32
Fig S24 Comparison of the experimental INS spectra of all butene isomers and reacted GVL at 320 degC
0 200 400 600 800 1000 1200 1400 1600
S(Q
) (a
u)
Neutron energy loss (cm-1)
Reaction 320 oC
trans-2-butene
i-butene
1-butene
cis-2-butene
0 20 40 60 80 100 120 140 160 180 200
Neutron energy loss (meV)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
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and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
33
Supplementary Tables
Table S1 Textural properties (data determined from N2 sorption isotherms at 77 K) and crystallite size (data
determined from SEM) of all zeolites used in this study
Samples ABET (m2 g-1)a Amic (m2 g-1) b Aext (m2 g-1) c Vmic (cm3 g-1) d Vtotal (cm3 g-1) e
Crystallite sizef
(nm)
HZSM-5 (00271) 413 314 99 019 033 200-500
HZSM-5 (0041) 346 259 87 015 028 200-500
HZSM-5 (00671) 348 277 71 016 026 200-500
NbS-1 (00271) 377 284 93 017 029 300-500
NbS-1 (0041) 357 282 75 016 027 300-500
NbAlS-1(00270041) 408 263 145 018 041 300-500
NbAlS-1(00400271) 376 268 108 017 033 300-500
HZSM-5 (0041)g 338 258 80 015 027 200-500
NbAlS-1(00270041)g 396 262 134 018 039 300-500
aBET specific surface area bMicropore surface area cExternal surface area dMicropore volume eTotal pore volume fObtainted from SEM gUsed catalyst
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
34
Table S2 Spin-Hamiltonian parameters of radiation induced Nb(IV) and electron hole Al-O-Si defects
from simulation of CW X-band EPR spectra in Fig 1 lw is the homogeneous Lorentzian linewidth g and A
are the principle values of the g and hyperfine interaction tensors
Signal Parameters
Electron
Spin
Nuclear
Spin g-tensor g-Strain
A-tensor
(G)
lw
(mT)
Nb defect 12 92 [1935 1935 1866] [004 004 00] [159 159
310] [0 40]
Al defect 12 52 [20012 2007 2045] [00 0003 004] [7 7 -] [00 04]
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
35
Table S3 Summary of acidity of all zeolites used in this work Data were determined by NH3-TPD and
Pyridine-IR studies
Catalyst Weak acida
(mmol g-1)
Strong acida
(mmol g-1)
Total acida
(mmol g-1)
LB acid
ratiob
HZSM-5(00271) 015 025 04 039
HZSM-5(0041) 024 028 052 037
HZSM-5(00671) 033 03 063 027
NbS-1(00271) 004 0 004 -
NbS-1(0041) 004 0 004 -
NbAlS-1(00270041) 022 0 022 469
NbAlS-1(00400271) 023 0 023 35 aFrom NH3-TPD bFrom Pyridine-IR
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
36
Table S4 The butenes distribution in equilibrium at 320 degC and the distribution of butene isomers produced
from conversion of 30 GVL at 320 degC over catalysts
Catalyst Distribution ()
i-butene 1-butene trans-2-butene cis-2-butene
Equilibrium27 45 12 27 16
HZSM-5(0041) 44 14 25 17
NbAlS-1(00270041) 18 19 38 25
NbOPO4 15 20 39 26
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
37
Table S5 Comparison of the catalytic performance of reported catalysts for the conversion of GVL in aqueous solution (25-40 wt ) to butenes
Catalyst Reaction Conditions GVL
concentration
(wt )
GVL
conversion
()
Butene
Yield
(mol )a
Ref
Temperature
(degC)
WHSV
(h-1)
Pressure
(bar)
NbAlS-1(00270041) 320 018 1 30 100 993 this work
SiO2Al2O3 375 09 1 30 97 75 28
HZSM-5(0041) 320 018 1 30 76 232 this work
LaZSM-5 450 1 10 40 gt99 ca 21 15
PdNb2O5b 275 05 14 30d 100 lt16c 29
Zn-AlPO-5 397 077 10 40 65 ca 12 30
H3PO4 240 - - 25 100 12c 31
ZnZSM-5 450 1 10 40 gt99 ca 6 15
AlPO-5 397 077 10 40 2 ca 04 30
aButene yield is calculated by the equation defined in the Method section
bunder H2 atmosphere
cThe product includes both butene and butane d002 M H2SO4 was added in the GVL solution
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
38
Table S6 1st Shell fitting of EXAFS data for as-prepared and GVL-adsorbed NbS-1 and NbAlS-1
R (Aring)a σ a Amp a CN a
NbAlS-1 (Dry) Nb=O 1680 0017 082 1 Nb-O 2014 0008 082 3 NbAlS-1
Nb=O 1721 0012 078 1
Nb-O 2014 0004 078 3
NbAlS-1+GVL
Nb=O 1943 0003 075 1
Nb-O 2014 0010 075 3
NbS-1
Nb=O 1711 0032 091 1
Nb-O 2014 0005 091 3
NbS-1+GVL
Nb=O 1770 0004 089 1
Nb-O 2014 0014 089 3 aR = Interatomic distance from central scattering atom σ = Debye-Waller factor Amp = amplitude factor
and CN = coordination number
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
39
Table S7 Crystallographic data and details of NbAlS-1and zeolites samples after GVL adsorption
Samples GVLHZSM-5(0041) GVLNbS-1(00271) NbAlS-1(00270041) GVLNbAlS-1(00270041)
Crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic
Space group Pnma Pnma Pnma Pnma
Chemical formula Al3692Si92308O192 8GVL Nb2524Si93476O192 8GVL Al3599Nb2429Si89972O192 Al3599Nb2429Si89972O192 8GVL
2θ range for refinement (deg) 3 ndash 50 3 ndash 50 3 ndash 50 3 ndash 50
Detector Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals Multi-analyser crystals
Number of hkls 3251 3214 3179 3222
Refinement methods Rietveld Rietveld Rietveld Rietveld
a (Aring) 201351(2) 200604(2) 199955(3) 200697(3)
b (Aring) 199852(2) 198995(1) 198333(3) 199150(3)
c (Aring) 134549(2) 134010(1) 133531(2) 134214(2)
V (Aring3) 541428(11) 534957(7) 529553(15) 536437(15)
RwpRexp Rp () 445135013378 463131253497 553133614058 444933763305
Wavelength (Aring) 082487(1) 082487(1) 082487(1) 082487(1)
Gof χ2 1272 1482 1646 1318
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
40
Table S8 Atomic parameters from the Rietveld refinement of GVLHZSM-5(0041) at room
temperature
Species Atom x y z SOF Beq(Aring2) Wyckoff
HZSM-5(0041) Al1 -00732(5) 00570(7) 08366(7) 003846154 100(5) 8d
Al2 01869(6) -00339(5) 03189(8) 003846154 100(5) 8d
Al3 02207(5) -00626(7) 05256(8) 003846154 100(5) 8d
Al4 01210(5) 00590(7) 10220(8) 003846154 100(5) 8d
Al5 -00703(6) -00272(5) 01933(8) 003846154 100(5) 8d
Al6 01859(5) 00593(6) 06679(8) 003846154 100(5) 8d
Al7 -00745(6) 06734(6) 08243(9) 003846154 100(5) 8d
Al8 01956(6) 01297(5) 03114(7) 003846154 100(5) 8d
Al9 02187(5) 01761(5) 05326(8) 003846154 100(5) 8d
Al10 01228(5) 06749(6) 10400(8) 003846154 100(5) 8d
Al11 -00694(6) 01308(6) 01819(9) 003846154 100(5) 8d
Al12 01859(6) 06714(5) 06756(8) 003846154 100(5) 8d
Si1 -00732(5) 00570(7) 08366(7) 09615385 100(5) 8d
Si2 01869(6) -00339(5) 03189(8) 09615385 100(5) 8d
Si3 02207(5) -00626(7) 05256(8) 09615385 100(5) 8d
Si4 01210(5) 00590(7) 10220(8) 09615385 100(5) 8d
Si5 -00703(6) -00272(5) 01933(8) 09615385 100(5) 8d
Si6 01859(5) 00593(6) 06679(8) 09615385 100(5) 8d
Si7 -00745(6) 06734(6) 08243(9) 09615385 100(5) 8d
Si8 01956(6) 01297(5) 03114(7) 09615385 100(5) 8d
Si9 02187(5) 01761(5) 05326(8) 09615385 100(5) 8d
Si10 01228(5) 06749(6) 10400(8) 09615385 100(5) 8d
Si11 -00694(6) 01308(6) 01819(9) 09615385 100(5) 8d
Si12 01859(6) 06714(5) 06756(8) 09615385 100(5) 8d
O1 01189(10) -00643(12) 02762(13) 1 143(9) 8d
O2 01900(11) -00665(10) 04093(13) 1 143(9) 8d
O3 02017(11) 00485(12) 10198(11) 1 143(9) 8d
O4 -00964(9) -00573(13) 10736(15) 1 143(9) 8d
O5 01132(9) 00573(12) 07009(13) 1 143(9) 8d
O6 02544(10) 00574(13) 07592(13) 1 143(9) 8d
O7 01249(11) 01569(12) 02676(15) 1 143(9) 8d
O8 01995(12) 01482(9) 04331(13) 1 143(9) 8d
O9 01968(12) 06607(9) 00500(12) 1 143(9) 8d
O10 -00922(10) 01564(11) 10827(17) 1 143(9) 8d
O11 01123(10) 06498(11) 07436(14) 1 143(9) 8d
O12 02420(11) 06557(12) 07396(15) 1 143(9) 8d
O13 02109(9) 00468(11) 03170(12) 1 143(9) 8d
O14 -00793(8) 00525(13) 01708(13) 1 143(9) 8d
O15 -00850(10) 01327(12) 08874(17) 1 143(9) 8d
O16 -01009(10) 00004(11) 09239(15) 1 143(9) 8d
O17 -01006(10) 06343(12) -00444(14) 1 143(9) 8d
O18 01746(10) 01273(11) 06145(13) 1 143(9) 8d
O19 01980(12) 00019(10) 06091(12) 1 143(9) 8d
O20 02014(13) 06300(11) 05761(13) 1 143(9) 8d
O21 -00054(11) 00405(12) 07595(12) 1 143(9) 8d
O22 -00045(12) 06580(13) 07876(13) 1 143(9) 8d
O23 -00801(15) 075 0861(2) 1 143(9) 4c
O24 01839(17) 075 0648(2) 1 143(9) 4c
O25 02011(18) 025 0563(2) 1 143(9) 4c
O26 00863(13) 075 0143(2) 1 143(9) 4c
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
41
GVLI O1 -00251(15) 08553(18) -0468(2) 0500(3) 06(4) 8d
O2 -0013(2) 07533(17) -0531(3) 0500(3) 06(4) 8d
C1 00570(11) 08446(12) -05861(14) 0500(3) 06(4) 8d
C2 00466(18) 09175(12) -05663(18) 0500(3) 06(4) 8d
C3 0004(2) 09222(15) -0484(2) 0500(3) 06(4) 8d
C4 00038(13) 08112(15) -05293(19) 0500(3) 06(4) 8d
C5 -0034(3) 09728(19) -0448(3) 0500(3) 06(4) 8d
H1a 00999(11) 08315(15) -05641(17) 0500(3) 07(5) 8d
H1b 00528(13) 08360(13) -06553(15) 0500(3) 07(5) 8d
H2a 0088(2) 09384(14) -0553(2) 0500(3) 07(5) 8d
H2b 0026(2) 09378(15) -0622(2) 0500(3) 07(5) 8d
H3 0038(2) 09204(15) -04313(18) 0500(3) 07(5) 8d
H5a -0043(3) 0965(2) -0380(3) 0500(3) 07(5) 8d
H5b -0011(4) 10138(17) -0454(3) 0500(3) 07(5) 8d
H5c -0074(3) 0975(3) -0485(3) 0500(3) 07(5) 8d
GVLII O1 -03289(15) -0778(2) -02817(19) 0500(4) 06(4) 8d
O2 -04372(14) -0757(2) -02733(16) 0500(4) 06(4) 8d
C1 -03730(11) -07204(15) -04150(12) 0500(4) 06(4) 8d
C2 -02990(11) -0718(2) -04230(16) 0500(4) 06(4) 8d
C3 -02738(13) -0762(3) -0350(2) 0500(4) 06(4) 8d
C4 -03856(13) -07518(18) -03175(14) 0500(4) 06(4) 8d
C5 -02129(14) -0768(4) -0308(3) 0500(4) 06(4) 8d
H1a -03908(13) -07461(16) -04681(13) 0500(3) 07(5) 8d
H1b -03904(14) -06762(15) -04174(16) 0500(3) 07(5) 8d
H2a -02856(13) -0732(2) -04875(17) 0500(3) 07(5) 8d
H2b -02835(15) -0674(2) -04093(19) 0500(3) 07(5) 8d
H3 -0275(2) -0803(3) -0389(3) 0500(3) 07(5) 8d
H5a -0208(2) -0812(4) -0281(3) 0500(3) 07(5) 8d
H5b -01797(13) -0762(4) -0357(3) 0500(3) 07(5) 8d
H5c -02080(14) -0735(4) -0257(3) 0500(3) 07(5) 8d
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
42
Table S9 Atomic parameters from the Rietveld refinement of GVLNbS-1(00271) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbS-1(00271) Nb1 09251(6) 00572(8) 08328(9) 002629 227(5) 8d
Nb2 01931(7) 09694(5) 03188(9) 002629 227(5) 8d
Nb3 02217(5) 09372(7) 05309(9) 002629 227(5) 8d
Nb4 01213(6) 00637(8) 00277(9) 002629 227(5) 8d
Nb5 09244(6) 09679(6) 01908(9) 002629 227(5) 8d
Nb6 01872(6) 00598(7) 06750(9) 002629 227(5) 8d
Nb7 09247(6) 06704(6) 08254(10) 002629 227(5) 8d
Nb8 01894(7) 01293(6) 03064(8) 002629 227(5) 8d
Nb9 02224(6) 01748(5) 05331(9) 002629 227(5) 8d
Nb10 01200(6) 06732(6) 00323(10) 002629 227(5) 8d
Nb11 09314(6) 01316(7) 01817(10) 002629 227(5) 8d
Nb12 01877(7) 06731(5) 06788(9) 002629 227(5) 8d
Si1 09251(6) 00572(8) 08328(9) 097371 227(5) 8d
Si2 01931(7) 09694(5) 03188(9) 097371 227(5) 8d
Si3 02217(5) 09372(7) 05309(9) 097371 227(5) 8d
Si4 01213(6) 00637(8) 00277(9) 097371 227(5) 8d
Si5 09244(6) 09679(6) 01908(9) 097371 227(5) 8d
Si6 01872(6) 00598(7) 06750(9) 097371 227(5) 8d
Si7 09247(6) 06704(6) 08254(10) 097371 227(5) 8d
Si8 01894(7) 01293(6) 03064(8) 097371 227(5) 8d
Si9 02224(6) 01748(5) 05331(9) 097371 227(5) 8d
Si10 01200(6) 06732(6) 00323(10) 097371 227(5) 8d
Si11 09314(6) 01316(7) 01817(10) 097371 227(5) 8d
Si12 01877(7) 06731(5) 06788(9) 097371 227(5) 8d
O1 01221(11) 09496(15) 02756(15) 1 174(9) 8d
O2 01978(13) 09454(13) 04211(15) 1 174(9) 8d
O3 01972(12) 00471(12) 00272(12) 1 174(9) 8d
O4 09056(10) 09378(13) 00716(16) 1 174(9) 8d
O5 01130(10) 00568(14) 07093(14) 1 174(9) 8d
O6 02454(11) 00533(17) 07497(15) 1 174(9) 8d
O7 01269(12) 01530(13) 02687(17) 1 174(9) 8d
O8 01911(12) 01511(10) 04246(14) 1 174(9) 8d
O9 01937(13) 06600(9) 00337(13) 1 174(9) 8d
O10 09020(10) 01555(12) 00856(17) 1 174(9) 8d
O11 01074(11) 06549(13) 07344(16) 1 174(9) 8d
O12 02450(13) 06634(12) 07479(18) 1 174(9) 8d
O13 01960(11) 00507(12) 03194(12) 1 174(9) 8d
O14 09235(9) 00522(14) 01839(14) 1 174(9) 8d
O15 09150(11) 01320(12) 08870(18) 1 174(9) 8d
O16 09038(12) 09941(11) 09369(16) 1 174(9) 8d
O17 09046(11) 06318(12) 09459(16) 1 174(9) 8d
O18 01831(12) 01256(10) 06123(15) 1 174(9) 8d
O19 01896(14) 00034(11) 06007(14) 1 174(9) 8d
O20 01988(14) 06274(12) 05850(14) 1 174(9) 8d
O21 09968(11) 00530(16) 07598(12) 1 174(9) 8d
O22 09926(12) 06533(12) 07892(14) 1 174(9) 8d
O23 09115(16) 075 0857(2) 1 174(9) 4c
O24 0190(2) 075 0646(2) 1 174(9) 4c
O25 02087(16) 025 0560(2) 1 174(9) 4c
O26 00950(14) 075 0110(2) 1 174(9) 4c
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
43
GVLI O1 -0025(2) 0846(2) 0528(2) 0500(3) 38(6) 8d
O2 -0027(3) 0740(2) 0474(3) 0500(3) 38(6) 8d
C1 00385(12) 08245(13) 03876(14) 0500(3) 38(6) 8d
C2 0035(3) 08989(13) 04020(19) 0500(3) 38(6) 8d
C3 0005(3) 09101(16) 0496(2) 0500(3) 38(6) 8d
C4 -00075(16) 07972(18) 04634(18) 0500(3) 38(6) 8d
C5 -0025(5) 0965(2) 0536(3) 0500(3) 38(6) 8d
H1a 00829(13) 0809(2) 03975(17) 0500(3) 46(7) 8d
H1b 00242(14) 08132(16) 03221(15) 0500(3) 46(7) 8d
H2a 0079(3) 09175(19) 0400(2) 0500(3) 46(7) 8d
H2b 0008(3) 09184(18) 0352(2) 0500(3) 46(7) 8d
H3 0045(4) 09082(19) 0537(2) 0500(3) 46(7) 8d
H5a -0024(5) 0961(2) 0607(3) 0500(3) 46(7) 8d
H5b -0000(6) 10039(17) 0519(3) 0500(3) 46(7) 8d
H5c -0069(5) 0968(3) 0513(3) 0500(3) 46(7) 8d
GVLII O1 06915(19) 0222(2) 07132(18) 0499(4) 38(6) 8d
O2 05885(15) 0256(3) 0678(2) 0499(4) 38(6) 8d
C1 06792(13) 02780(16) 05633(11) 0499(4) 38(6) 8d
C2 07520(13) 0271(3) 05843(17) 0499(4) 38(6) 8d
C3 07582(17) 0228(3) 06677(19) 0499(4) 38(6) 8d
C4 06465(15) 0253(2) 06548(15) 0499(4) 38(6) 8d
C5 0809(2) 0217(4) 0733(3) 0499(4) 38(6) 8d
H1a 06675(16) 02519(18) 05066(14) 0500(3) 46(7) 8d
H1b 06686(17) 03239(17) 05516(16) 0500(3) 46(7) 8d
H2a 07739(15) 0252(3) 05277(19) 0500(3) 46(7) 8d
H2b 07704(17) 0313(3) 0601(2) 0500(3) 46(7) 8d
H3 0758(3) 0185(3) 0632(3) 0500(3) 46(7) 8d
H5a 0803(3) 0174(4) 0763(3) 0500(3) 46(7) 8d
H5b 08499(19) 0216(5) 0697(3) 0500(3) 46(7) 8d
H5c 0809(2) 0251(5) 0782(2) 0500(3) 46(7) 8d
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
44
Table S10 Atomic parameters from the Rietveld refinement of NbAlS-1(00270041) at room
temperature
Species Atom x y z SOF Beq (Aring2) Wyckoff
NbAlS-1
(00270041)
Al1 -00754(10) 00561(13) 08359(14) 003748828 305(9) 8d
Al2 01890(12) -00286(8) 03153(14) 003748828 305(9) 8d
Al3 02210(8) -00584(12) 05262(13) 003748828 305(9) 8d
Al4 01258(8) 00583(13) 10381(14) 003748828 305(9) 8d
Al5 -00785(10) -00393(11) 01783(15) 003748828 305(9) 8d
Al6 01840(10) 00571(12) 06827(14) 003748828 305(9) 8d
Al7 -00778(10) 06746(10) 08244(17) 003748828 305(9) 8d
Al8 01913(12) 01344(10) 03222(14) 003748828 305(9) 8d
Al9 02246(10) 01762(9) 05333(14) 003748828 305(9) 8d
Al10 01123(9) 06767(10) 10236(15) 003748828 305(9) 8d
Al11 -00658(9) 01323(11) 01756(15) 003748828 305(9) 8d
Al12 01888(11) 06738(9) 06779(14) 003748828 305(9) 8d
Nb1 -00754(10) 00561(13) 08359(14) 002530459 305(9) 8d
Nb2 01890(12) -00286(8) 03153(14) 002530459 305(9) 8d
Nb3 02210(8) -00584(12) 05262(13) 002530459 305(9) 8d
Nb4 01258(8) 00583(13) 10381(14) 002530459 305(9) 8d
Nb5 -00785(10) -00393(11) 01783(15) 002530459 305(9) 8d
Nb6 01840(10) 00571(12) 06827(14) 002530459 305(9) 8d
Nb7 -00778(10) 06746(10) 08244(17) 002530459 305(9) 8d
Nb8 01913(12) 01344(10) 03222(14) 002530459 305(9) 8d
Nb9 02246(10) 01762(9) 05333(14) 002530459 305(9) 8d
Nb10 01123(9) 06767(10) 10236(15) 002530459 305(9) 8d
Nb11 -00658(9) 01323(11) 01756(15) 002530459 305(9) 8d
Nb12 01888(11) 06738(9) 06779(14) 002530459 305(9) 8d
Si1 -00754(10) 00561(13) 08359(14) 09372071 305(9) 8d
Si2 01890(12) -00286(8) 03153(14) 09372071 305(9) 8d
Si3 02210(8) -00584(12) 05262(13) 09372071 305(9) 8d
Si4 01258(8) 00583(13) 10381(14) 09372071 305(9) 8d
Si5 -00785(10) -00393(11) 01783(15) 09372071 305(9) 8d
Si6 01840(10) 00571(12) 06827(14) 09372071 305(9) 8d
Si7 -00778(10) 06746(10) 08244(17) 09372071 305(9) 8d
Si8 01913(12) 01344(10) 03222(14) 09372071 305(9) 8d
Si9 02246(10) 01762(9) 05333(14) 09372071 305(9) 8d
Si10 01123(9) 06767(10) 10236(15) 09372071 305(9) 8d
Si11 -00658(9) 01323(11) 01756(15) 09372071 305(9) 8d
Si12 01888(11) 06738(9) 06779(14) 09372071 305(9) 8d
O1 01274(18) -0066(2) 0251(2) 1 223(15) 8d
O2 01862(18) -00622(19) 0426(2) 1 223(15) 8d
O3 02006(17) 0057(2) 10301(18) 1 223(15) 8d
O4 -01059(16) -00699(18) 1074(3) 1 223(15) 8d
O5 01138(17) 0051(2) 0721(2) 1 223(15) 8d
O6 02484(18) 0045(2) 0744(2) 1 223(15) 8d
O7 01323(19) 01542(19) 0272(3) 1 223(15) 8d
O8 02054(19) 01512(17) 0430(2) 1 223(15) 8d
O9 01978(19) 06575(13) 0011(2) 1 223(15) 8d
O10 -00893(17) 01552(18) 1079(3) 1 223(15) 8d
O11 01100(18) 06488(19) 0744(2) 1 223(15) 8d
O12 02379(18) 06545(18) 0782(3) 1 223(15) 8d
O13 01998(19) 00637(16) 0315(2) 1 223(15) 8d
O14 -00726(15) 00356(17) 0165(2) 1 223(15) 8d
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
45
O15 -00776(17) 01184(18) 0878(3) 1 223(15) 8d
O16 -00937(19) -00147(17) 0915(3) 1 223(15) 8d
O17 -01100(16) 06315(18) -0044(2) 1 223(15) 8d
O18 0194(2) 01298(18) 0614(3) 1 223(15) 8d
O19 0195(3) 00046(16) 0597(2) 1 223(15) 8d
O20 0191(2) 06358(18) 0576(2) 1 223(15) 8d
O21 -00033(19) 0054(3) 0792(2) 1 223(15) 8d
O22 -00138(17) 06582(18) 0786(2) 1 223(15) 8d
O23 -0100(2) 075 0866(4) 1 223(15) 4c
O24 0180(2) 075 0627(4) 1 223(15) 4c
O25 0230(2) 025 0623(4) 1 223(15) 4c
O26 0095(2) 075 0099(4) 1 223(15) 4c
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
46
Table S11 Atomic parameters from the Rietveld refinement of GVLNbAlS-1(00270041) at
room temperature
Species Atom x y z SOF Beq (Aring2) Wyckof
f
NbAlS-1
(00270041)
Al1 -00749(8) 00601(11) 08387(12) 0037488 276(9) 8d
Al2 01940(10) -00293(8) 03263(13) 0037488 276(9) 8d
Al3 02201(7) -00588(11) 05273(12) 0037488 276(9) 8d
Al4 01234(8) 00573(12) 10237(13) 0037488 276(9) 8d
Al5 -00797(9) -00368(10) 01959(13) 0037488 276(9) 8d
Al6 01840(10) 00634(10) 06792(12) 0037488 276(9) 8d
Al7 -00679(9) 06710(9) 08173(14) 0037488 276(9) 8d
Al8 01903(10) 01354(9) 03122(12) 0037488 276(9) 8d
Al9 02238(9) 01728(9) 05286(12) 0037488 276(9) 8d
Al10 01149(9) 06840(9) 10430(12) 0037488 276(9) 8d
Al11 -00742(9) 01348(10) 01767(14) 0037488 276(9) 8d
Al12 01915(10) 06726(8) 06722(12) 0037488 276(9) 8d
Nb1 -00749(8) 00601(11) 08387(12) 0025305 276(9) 8d
Nb2 01940(10) -00293(8) 03263(13) 0025305 276(9) 8d
Nb3 02201(7) -00588(11) 05273(12) 0025305 276(9) 8d
Nb4 01234(8) 00573(12) 10237(13) 0025305 276(9) 8d
Nb5 -00797(9) -00368(10) 01959(13) 0025305 276(9) 8d
Nb6 01840(10) 00634(10) 06792(12) 0025305 276(9) 8d
Nb7 -00679(9) 06710(9) 08173(14) 0025305 276(9) 8d
Nb8 01903(10) 01354(9) 03122(12) 0025305 276(9) 8d
Nb9 02238(9) 01728(9) 05286(12) 0025305 276(9) 8d
Nb10 01149(9) 06840(9) 10430(12) 0025305 276(9) 8d
Nb11 -00742(9) 01348(10) 01767(14) 0025305 276(9) 8d
Nb12 01915(10) 06726(8) 06722(12) 0025305 276(9) 8d
Si1 -00749(8) 00601(11) 08387(12) 0937207 276(9) 8d
Si2 01940(10) -00293(8) 03263(13) 0937207 276(9) 8d
Si3 02201(7) -00588(11) 05273(12) 0937207 276(9) 8d
Si4 01234(8) 00573(12) 10237(13) 0937207 276(9) 8d
Si5 -00797(9) -00368(10) 01959(13) 0937207 276(9) 8d
Si6 01840(10) 00634(10) 06792(12) 0937207 276(9) 8d
Si7 -00679(9) 06710(9) 08173(14) 0937207 276(9) 8d
Si8 01903(10) 01354(9) 03122(12) 0937207 276(9) 8d
Si9 02238(9) 01728(9) 05286(12) 0937207 276(9) 8d
Si10 01149(9) 06840(9) 10430(12) 0937207 276(9) 8d
Si11 -00742(9) 01348(10) 01767(14) 0937207 276(9) 8d
Si12 01915(10) 06726(8) 06722(12) 0937207 276(9) 8d
O1 01254(16) -0058(2) 0269(2) 1 219(14) 8d
O2 01765(15) -0047(2) 0430(2) 1 219(14) 8d
O3 01958(18) 00612(16) 10243(18) 1 219(14) 8d
O4 -00994(14) -0051(2) 1083(2) 1 219(14) 8d
O5 01199(16) 0056(2) 0722(2) 1 219(14) 8d
O6 02541(15) 0058(3) 0749(2) 1 219(14) 8d
O7 01266(17) 01583(19) 0270(2) 1 219(14) 8d
O8 02009(17) 01568(17) 0430(2) 1 219(14) 8d
O9 01964(17) 06527(13) 00417(18) 1 219(14) 8d
O10 -00930(16) 01626(18) 1066(3) 1 219(14) 8d
O11 01002(14) 06398(16) 0709(2) 1 219(14) 8d
O12 02354(15) 06516(18) 0758(2) 1 219(14) 8d
O13 02055(15) 00562(18) 03224(19) 1 219(14) 8d
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
47
O14 -00770(13) 0047(2) 0183(2) 1 219(14) 8d
O15 -00723(14) 01326(19) 0881(2) 1 219(14) 8d
O16 -00979(18) -00068(18) 0934(3) 1 219(14) 8d
O17 -01019(16) 06129(15) -0055(3) 1 219(14) 8d
O18 01832(17) 01254(17) 0612(2) 1 219(14) 8d
O19 01997(19) 00041(17) 0611(2) 1 219(14) 8d
O20 01782(16) 06396(16) 0589(2) 1 219(14) 8d
O21 -00018(17) 0058(2) 0793(2) 1 219(14) 8d
O22 -00057(15) 0643(2) 0756(2) 1 219(14) 8d
O23 -0094(2) 075 0823(3) 1 219(14) 4c
O24 0180(2) 075 0616(3) 1 219(14) 4c
O25 0203(2) 025 0580(3) 1 219(14) 4c
O26 0086(2) 075 0130(3) 1 219(14) 4c
GVLI O1 -0026(4) 0852(4) -0450(3) 0500(5) 24(8) 8d
O2 -0033(7) 0746(4) -0501(4) 0500(5) 24(8) 8d
C1 00205(19) 0831(2) -0604(2) 0500(5) 00205(19) 8d
C2 0018(6) 0905(2) -0590(3) 0500(5) 0018(6) 8d
C3 -0001(8) 0917(3) -0491(3) 0500(5) -0001(8) 8d
C4 -0016(3) 0803(3) -0517(3) 0500(5) 24(8) 8d
C5 -0027(13) 0971(4) -0444(4) 0500(5) 24(8) 8d
H1a 0066(2) 0816(4) -0606(3) 0500(5) 29(9) 8d
H1b -0001(2) 0819(3) -0665(2) 0500(5) 29(9) 8d
H2a 0060(8) 0924(4) -0604(4) 0500(5) 29(9) 8d
H2b -0015(8) 0924(4) -0633(3) 0500(5) 29(9) 8d
H3 0043(8) 0916(4) -0460(3) 0500(5) 29(9) 8d
H5a -0018(13) 0968(4) -0374(4) 0500(5) 29(9) 8d
H5b -0005(16) 1010(3) -0468(5) 0500(5) 29(9) 8d
H5c -0073(13) 0974(7) -0455(5) 0500(5) 29(9) 8d
GVLII O1 -0330(2) -0780(4) -0294(2) 0500(6) 24(8) 8d
O2 -0438(2) -0771(4) -0327(3) 0500(6) 24(8) 8d
C1 -03553(19) -0731(2) -04448(16) 0500(6) 24(8) 8d
C2 -0283(2) -0721(4) -0426(2) 0500(6) 24(8) 8d
C3 -0266(2) -0761(4) -0342(3) 0500(6) 24(8) 8d
C4 -0381(2) -0761(3) -0352(2) 0500(6) 24(8) 8d
C5 -0214(2) -0760(6) -0278(3) 0500(6) 24(8) 8d
H1a -0362(2) -0760(3) -0501(2) 0500(5) 29(9) 8d
H1b -0376(2) -0689(3) -0457(2) 0500(5) 29(9) 8d
H2a -0258(2) -0735(4) -0483(3) 0500(5) 29(9) 8d
H2b -0274(3) -0676(4) -0411(3) 0500(5) 29(9) 8d
H3 -0257(3) -0803(4) -0376(4) 0500(5) 29(9) 8d
H5a -0210(3) -0802(7) -0247(4) 0500(5) 29(9) 8d
H5b -0174(2) -0752(7) -0315(4) 0500(5) 29(9) 8d
H5c -0220(3) -0725(7) -0230(3) 0500(5) 29(9) 8d
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
48
Table S12 Displaying the interatomic distances between the adsorption site and framework atoms
from the Rietveld refinements of the corresponding SXPD data at 25 degC
Interatomic
distances (Aring)
NbAlS-1(00270041) HZSM-5(0041) NbS-1(00271)
O1GVLI O2GVLI O1GVLII O2GVLII O2GVLI O2GVLII O1GVLI O1GVLII
T1 5758(68) 5887(58) 5577(33) 5940(40)
T2 5157(79) 4697(71) 5393(40) 4478(41)
T3 5258(82) 4998(60) 5271(42) 4875(36)
T4 6310(53) 4569(63) 6512(32) 4725(36)
T5 5353(54) 4076(76) 5228(33) 4447(41)
T6 4728(69) 3490(75) 4637(38) 3560(40)
T7 3713(48) 5689(37) 4124(31) 5788(31)
T8 3789(75) 6695(37) 4005(39) 6697(28)
T9 4137(80) 3839(37) 4065(41) 3581(29)
T10 7231(52) 5523(41) 7177(42) 5184(35)
T11 4191(56) 7299(42) 4343(33) 7468(42)
T12 4689(79) 6170(43) 4737(40) 5867(30)
O1 5801(103) 5235(70) 5203(43) 5160(41)
O2 5852(120) 6526(65) 5507(43) 6369(38)
O3 7711(134) 5039(68) 7446(45) 5825(39)
O4 6930(75) 3820(85) 6742(44) 4298(44)
O5 5114(89) 3900(82) 4860(43) 3969(45)
O6 6692(114) 5250(75) 6882(44) 5355(41)
O7 4024(90) 6246(51) 4567(45) 6983(31)
O8 3927(131) 6183(52) 4440(45) 5667(32)
O9 5819(138) 5684(55) 6096(46) 5930(35)
O10 6576(84) 4660(58) 6643(46) 5483(34)
O11 4423(103) 7248(52) 4875(44) 7626(31)
O12 5981(120) 7237(51) 6552(45) 7606(32)
O13 5659(109) 7351(75) 6335(43) 7393(41)
O14 6229(86) 5506(89) 6481(44) 5963(47)
O15 5965(80) 3388(64) 5664(46) 4009(38)
O16 7647(79) 5513(78) 7579(43) 6203(41)
O17 6691(75) 3918(68) 7143(44) 4313(34)
O18 4132(119) 4301(61) 4189(44) 3870(37)
O19 6048(107) 6009(73) 6238(42) 5959(41)
O20 4890(131) 6536(54) 5114(46) 6651(36)
O21 5465(77) 3667(85) 5155(42) 4278(46)
O22 4050(71) 5961(53) 4642(44) 6259(30)
O23 4518(76) 4760(57) 5445(49) 4935(35)
O24 4555(139) 6483(57) 4639(52) 7173(40)
O25 3574(141) 4379(57) 3812(54) 3973(41)
O26 5499(88) 3055(57) 4821(48) 3210(38)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
49
Table S13 Summary of different types of Si atoms from the 29Si NMR data and (Al+Nb)Si ratio
Chemical Shift
(ppm) Assignment203233
Area () (Al+Nb)Si
by 29Si NMRa
(Al+Nb)Si
by EDX
HZSM-5 NbAlS-1 HZSM-5 NbAlS-1 HZSM-5 NbAlS-1
-112 to -117 Si(OSi)4 814 674
0037 0066
004 0067
-105 to 108 Si(OSi)3(OAlNb) 149 166
-102 Si(OSi)3(OH) 37 101
-98 Si(OSi)2(OAlNb)2 0 5
-92 Si(OSi)2(OH)2 0 09 a(Al+Nb)Si = 025[ ISi(1Al) + 2ISi(2Al)]I where ISi(1Al) and ISi(2Al) denotes the area of the NMR peak
corresponding to the Si(OSi)3(OAlNb) and Si(OSi)2(OAlNb)2 atoms respectively and I denotes the
total area of the 29Si NMR peaks1934
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
50
Table S14 Contents of different NbAlH sites on NbAlS-1(00270041)
Types of NbAl
distribution Types of species NbAlH sites Position Nb Position Al O attached H
29Si Chemical shift
(ppm)b
Weight
()c
NbAl adjacent
Species I
NbOSiOAl
(Fig4f)
1 T8 T9 O25
-98 3125 2 T8 T9 O8
3 T8 T9 O18
4 T8 T9 O9
Species II
NbOSiOSiOAl
(Fig4i)
5 T6 T10 O26
-105 3125 6 T6 T10 O15
7 T6 T10 O10
8 T6 T10 O9
NbAl non-
adjacent
Species III
NbO(SiO)nAla
9 T8 T12 O11 -105 5
10 T6 T7 O17
Isolated Al Species IV
(SiO)nAlO(SiO)na
11 - T2 O1 -105 325
12 - T4 O3 an ge 3 bobtained from 29Si NMR cCalculated based on NbAl ratio SXPD and Rietveld refinement results and 29Si NMR results
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
51
Table S15 Assignment of INS peaks of bare NbAlS-1
Wavenumber in
simulation (cm-1)
Wavenumber in
experiment (cm-1)
Vibrational mode
77 76 OH out-of-plane bending
157 148 Nb-O bending
209 219 OH out-of-plane bending
237 245 Zeolite framework
279 282 Zeolite framework + OH out-of-plane bending
317 331 Zeolite framework + OH out-of-plane bending
394 387 Zeolite framework + OH out-of-plane bending
418 416 Zeolite framework + OH out-of-plane bending
558 534 Zeolite framework
797 798 Zeolite framework
960 964 OH in-plane bending + Si-O stretching
1086 1090 OH in-plane bending
1191 1192 OH in-plane bending + Si-O stretching
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
52
Table S16 Assignment of INS peaks of GVL
Wavenumber in GVL
(or adsorbed GVL)
simulation (cm-1)a
Wavenumber in GVL
(adsorbed GVL)
experiment (cm-1)a
Vibrational modeb
141 (129) 151 (144) C4 wagging (weaker)
161 (158) 181 (173) O2-C1-C2 twisting (C2 wagging)
249 (205) 273 (234) C4-C5 torsion (weaker)
303 (303) 317 (308) C4-C5 rocking (weaker)
503 512 C1=O2 rocking
515 530 C1 wagging
592 609 Ring deformation
645 655 Ring deformation
785 802 Ring deformation
809 827 Ring stretching
913 899 Ring deformation
1043 (1037) 1060 (1046) C4-O1 stretching (weaker)
1101 (1106) 1127 (1121) C1-O1-C4 asymmetric stretching (weaker)
1170-1443 1196-1456 C-H bending aThe wavenumbers of vibration modes of adsorbed GVL are listed in parentheses bThe vibration modes of adsorbed GVL are listed in parentheses lsquoWeakerrsquo in parentheses means
vibrational mode does not change upon adsorption but only the vibrational intensity becomes weaker
C1
C2 C3
C4C5O2
O1
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
53
Supplementary References
1 Stoll S amp Schweiger A EasySpin a comprehensive software package for spectral simulation
and analysis in EPR J Magn Reson 178 42ndash55 (2006)
2 Clark S J et al First principles methods using CASTEP Z Fuumlr Krist - Cryst Mater 220 567ndash
570 (2005)
3 Refson K Tulip P R amp Clark S J Variational density-functional perturbation theory for
dielectrics and lattice dynamics Phys Rev B 73 155114 (2006)
4 Perdew J P Burke K amp Ernzerhof M Generalized gradient approximation made simple Phys
Rev Lett 77 3865ndash3868 (1996)
5 McNellis E R Meyer J amp Reuter K Azobenzene at coinage metal surfaces role of dispersive
van der Waals interactions Phys Rev B 80 205414 (2009)
6 Cheng Y Q Daemen L L Kolesnikov A I amp Ramirez-Cuesta A J Simulation of inelastic
neutron scattering spectra using OCLIMAX J Chem Theory Comput 15 1974ndash1982 (2019)
7 Ramirez-Cuesta A J aCLIMAX 401 The new version of the software for analyzing and
interpreting INS spectra Comput Phys Commun 157 226ndash238 (2004)
8 Hutter J Iannuzzi M Schiffmann F amp VandeVondele J cp2k atomistic simulations of
condensed matter systems Wiley Interdiscip Rev Comput Mol Sci 4 15ndash25 (2014)
9 Lippert B G Hutter J amp Parrinello M A hybrid Gaussian and plane wave density functional
scheme Mol Phys 92 477ndash488 (1997)
10 VandeVondele J et al Quickstep fast and accurate density functional calculations using a mixed
Gaussian and plane waves approach Comput Phys Commun 167 103ndash128 (2005)
11 VandeVondele J amp Hutter J Gaussian basis sets for accurate calculations on molecular systems
in gas and condensed phases J Chem Phys 127 114105 (2007)
12 Goedecker S Teter M amp Hutter J Separable dual-space Gaussian pseudopotentials Phys Rev
B 54 1703ndash1710 (1996)
13 Grimme S Antony J Ehrlich S amp Krieg H A consistent and accurate ab initio
parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J
Chem Phys 132 154104 (2010)
14 Yang S et al Supramolecular binding and separation of hydrocarbons within a functionalized
porous metalndashorganic framework Nat Chem 7 121ndash129 (2015)
15 Ye L et al Decarboxylation of lactones over ZnZSM-5 elucidation of the structure of the
active site and molecular interactions Angew Chem Int Ed 56 10711ndash10716 (2017)
16 Lo B T W et al Elucidation of adsorbate structures and interactions on Broslashnsted acid sites in
H-ZSM-5 by synchrotron X-ray powder diffraction Angew Chem Int Ed 55 5981ndash5984
(2016)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
54
17 Bond J Q Jungong C S amp Chatzidimitriou A Microkinetic analysis of ring opening and
decarboxylation of γ-valerolactone over silica alumina J Catal 344 640ndash656 (2016)
18 Xia Q et al Direct hydrodeoxygenation of raw woody biomass into liquid alkanes Nat
Commun 7 11162 (2016)
19 Sklenak S et al Aluminium siting in the ZSM-5 framework by combination of high resolution
27Al NMR and DFTMM calculations Phys Chem Chem Phys 11 1237ndash1247 (2009)
20 Zhang W et al Methane dehydro-aromatization over MoHZSM-5 in the absence of oxygen a
multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-
5 zeolite with different crystal sizes J Catal 188 393ndash402 (1999)
21 Lemishko T Valencia S Rey F Jimeacutenez-Ruiz M amp Sastre G Inelastic neutron scattering
study on the location of Broslashnsted acid sites in high silica LTA zeolite J Phys Chem C 120
24904ndash24909 (2016)
22 Lemishko T et al Inelastic neutron scattering study of the aluminum and Broslashnsted site location
in aluminosilicate LTA zeolites J Phys Chem C 122 11450ndash11454 (2018)
23 Parry E P An infrared study of pyridine adsorbed on acidic solids Characterization of surface
acidity J Catal 2 371ndash379 (1963)
24 Carniti P Gervasini A Bossola F amp Dal Santo V Cooperative action of Broslashnsted and Lewis
acid sites of niobium phosphate catalysts for cellobiose conversion in water Appl Catal B
Environ 193 93ndash102 (2016)
25 Post J G amp van Hooff J H C Acidity and activity of H-ZSM-5 measured with NH3-TPD and
n-hexane cracking Zeolites 4 9ndash14 (1984)
26 Kim S Park G Woo M H Kwak G amp Kim S K Control of hierarchical structure and
framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on
methanol conversion ACS Catal 9 2880ndash2892 (2019)
27 Butler A C amp Nicolaides C P Catalytic skeletal isomerization of linear butenes to isobutene
Catal Today 18 443ndash471 (1993)
28 Bond J Q Alonso D M Wang D West R M amp Dumesic J A Integrated catalytic
conversion of γ-valerolactone to liquid alkenes for transportation fuels Science 327 1110ndash1114
(2010)
29 Serrano-Ruiz J C Braden D J West R M amp Dumesic J A Conversion of cellulose to
hydrocarbon fuels by progressive removal of oxygen Appl Catal B Environ 100 184ndash189
(2010)
30 Lin W-C et al Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of
γ-valerolactone a new selective route for biomass conversion ChemSusChem 11 4214ndash4218
(2018)
31 Kang S et al One-pot production of hydrocarbon oils from biomass derived γ-valerolactone
Fuel 216 747ndash751 (2018)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)
55
32 Cheng Y Miao C Hua W Yue Y amp Gao Z CrZSM-5 for ethane dehydrogenation
enhanced catalytic activity through surface silanol Appl Catal Gen 532 111ndash119 (2017)
33 Fyfe C A Gobbi G C Klinowski J Thomas J M amp Ramdas S Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by solid-state NMR Nature
296 530ndash533 (1982)
34 Engelhardt G Lohse U Lippmaa E Tarmak M amp Maumlgi M 29Si-NMR-Untersuchungen zur
verteilung der silicium-und aluminiumatome im alumosilicatgitter von zeolithen mit Faujasit-
struktur Z Fuumlr Anorg Allg Chem 482 49ndash64 (1981)