Post on 09-Oct-2020
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Supplementary information
Phosphonate Functionalized Carbon Spheres as Brønsted Acid Catalysts
for Valorization of bio-renewable α-Pinene Oxide to trans-Carveol Amravati S. Singh a,b, Jacky H. Advani a,b,, and Ankush V. Biradar a,b,*aInorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals
Research Institute (CSIR-CSMCRI), G. B. Marg, Bhavnagar-364002, Gujarat, IndiabAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, Uttar Pradesh,
India
*Corresponding author: Tel.: +91 278 2567760 Ext: 7170; Fax: +91 278 2566970
Email: ankush@csmcri.res.in
This SI contains 10 pages, 1 table, 18 Figures
Contents Page No.
S1.
S2.
S3.
S4.
S5.
S6.
S7.
S8.
S9.
S10.
S11.
S12.
Material Characterizations
Scanning electron microscopy (SEM)
Solid 13C and 31P CP MAS NMR spectrum of CS(α) and PCS(γ)
XPS survey spectrum of PCS(α2)
Acidic strength calculations of PCS (α2) determine by ICP- OES
Effect of PCS(α2) amount on the distribution of the products in the
isomerization of α- pinene oxide
Recyclability of the catalyst PCS(α2)
The activity of the catalyst after Hot filtration test
SEM and EDAX images of recycled PCS (α2)1H and 13C NMR analysis of trans-Carveol
Fourier transform infrared spectroscopy (FT-IR) of trans-Carveol
GC-MS profile of the products obtained in the isomerization of α-
pinene oxide
2
3-4
5
5
5-6
6
6
7
7
7
8
9-10
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2020
2
S1. Materials characterizations
The structural characterization studies of the catalyst were carried out by different
physiochemical methods. The PXRD analysis was carried out using Philips X’pert MPD
system for powder X-ray Diffractometer. The black powder obtained was scanned in the range
of 10-80° using Cu Kα radiation of 1.54056 Å wavelength with a Ni filter. A Perkin-Elmer GX
spectrophotometer was used for the Fourier-transform infrared spectrophotometry (FTIR)
spectra using KBr pellets in the wavelength range of 400-4000 cm-1. The energy dispersive X-
ray (EDX) mapping and morphology of the catalyst was determined using a JEOL JSM 7100F
field emission scanning electron microscope (FE-SEM). The synthesized catalyst was
dispersed in isopropyl alcohol by sonication and was drop casted on a brass stub. The stub was
dried under vacuum and used for analysis. Transmission electron microscope (TEM) (JEOL
JEM 2100) was used to analyze the size and shape of the particles and recording the selected
area electron diffraction (SAED) of the sample. The samples were loaded on the TEM grid by
dispersing it in isopropyl alcohol using ultrasonicator and then drop-casting the suspension on
the TEM grid. This drop casted grid was dried in a vacuum oven before analysis. X-ray
photoelectron spectroscopy (XPS) was performed using an ESCA+ (Omicron Nanotechnology,
Germany) with a monochromatized Al-Kα X-ray (hν = 1486.7 eV) as the excitation source (15
kV and 20 mA). The pass energy for the survey spectrum was 50 eV and 20 eV in case of the
short scan. The sample was placed on the copper tape and degassed in the XPS FEL chamber
to minimize the air contamination. A charge neutralizer of 2 keV was used to overcome any
charging problem, and the calibration was done using the adventitious C 1s feature at 284.6 eV
as a reference. All the spectra’s were recorded at 90° of the X-ray source. 31P and 13C solid-
state nuclear resonance (NMR) spectroscopy was performed using a Bruker 11.7 T
spectrometer equipped with a triple resonance 2.5 mm solid-state probe head and an avance III
console. Samples were prepared for NMR by ultrasonic ion in acetone for 5 min, then dried at
80°C, and filled into a 2.5 mm zirconia rotor. All experiments were performed at room
temperature, either in static mode or while spinning the sample at 20kHz magic angle spinning
(MAS) frequency. The 31P chemical shift was determined with reference to 85% H3PO4 in D2O
and the 13C chemical shift was determined with reference to Si(CH3)4. The number of transients
recorded was 2000 for 31P NMR experiments, and 16000-24000 for 13C NMR experiments.
The classical Hahn echo pulse sequence was used for 31P NMR experiments, and a simple 30°-
one pulse excitation sequence was used for all 13C NMR and 31P NMR experiments (as
indicated). All spectra were acquired without decoupling. The recycle delay was set to 2s, the
3
echo delay to 0.2 ms, and the pulse length for 90° flip angle experiments to 5 µs for 31P NMR
experiments. The thermogravimetric analysis (TGA) was carried out on a Mettler TGA/DTA
851e instrument at a nitrogen flow rate of 50 mL/min. The surface area of the catalyst was
obtained using the ASAP 2010, Micromeritics Sorptometer at 7.4 K. The sample was degassed
at 150 ºC for 10h prior to sorption. ICP- OES analysis done by Perkin Elmer, optima, 2000
instrument.
S2. Scanning electron microscopy (SEM)
S2.1. SEM images of CS(α)
Fig. S1. Scanning electron microscopy (SEM) image of CS(α) (A-C).
S2.2. SEM images of PCS(α1)
Fig. S2: SEM images of PCS(α1) (A-D) and SEM elemental mapping of PCS(α1) where E
shows overall mapping, F- shows phosphorous, G-shows oxygen and H-shows carbon. And I
shows the SEM-EDAX of the sample. And Table shows the % availability of the elements.
4
S2.3. SEM and EDAX images of CS(γ)
Fig. S3. Scanning electron microscopy image of CS(γ) (A-D) and E show the SEM-EDAX of
the sample and Table shows the the % availability of the elements.
S2.4. SEM images of PCS(γ)
Fig. S4: Scanning electron microscopy (SEM) image of PCS(γ) (A-C) and D show the SEM-
EDAX of the sample. And Table shows the % availability of the elements.
5
S3. Solid 31P and 13C NMR of CS (γ) and PCS (γ)
-90-50-10205080120160f1 (ppm)
0.2
37
.62
18
.61
39
.75
-40-20020406080110140170200230f1 (ppm)
12.7
2
28.5
2
36.3
3
64.6
0
110.
62
150.
06
176.
64
209.
67
Fig. S5. (a) Solid-state 31P NMR of PCS (γ) (b) Comparison solid 13C NMR of CS (γ) and
PCS (γ).
S4: XPS survey spectrum of PCS (α2)
1200 1000 800 600 400 200 0
Inte
nsity
Binding Energy (E) (eV)
O1s
C1s
P2pP2s
Fig. S6. X-ray photoelectron spectroscopy (XPS) survey spectrum of PCS(α2).
S5: Acidic strength calculations of PCS (α2) determine by ICP- OES
The 100 mg of PCS(α2) catalyst was digested Aqua regia solution and analyzed by ICP-OES.
The P continent was found 1.33 wt%
Mole of P was calculated as fallows:
100 mg = 1.33 wt% of phosphorus
=1.33 mg phosphorus in 100 mg PCS(α2)
=13.3 mg phosphorus in 1000 mg PCS(α2)
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13.3 mg = 0.0133g phosphorus
Moles of phosphorus = Weight/Mol. Wt (MW of P-30.97)
= 0.0133/30.97
= 0.00042 moles/g
= 0.42 mmoles/g of phosphorus
S6. Table S1. Effect of PCS(α2) amount on the distribution of the products in the isomerisation
of α- pinene oxide.
Entry Selectivity (%)Weight
(mg)
Conv.
(%)TCV CPA TPC Others
1. 10 71 66 20 7 7
2. 20 80 66 21 7 6
3. 30 88 67 19 6 8
4. 40 94 67 20 7 6
Reaction condition: α- pinene oxide: 0.5 g (3.28 mmol); Catalyst: PCS (α2): Solvent: DMF (2
mL); Temp. : 140 °C; Time: 1 h.
S7. Recyclability of the catalyst PCS(α2)
100 98 96 95 9080
67 67 66 65 67 66
0 1 2 3 4 50
20
40
60
80
100
% C
onve
rsio
n/ S
elect
ivity
Recycle Time
% Conversion % Selectivity
Fig. S7. Recyclability of PCS(α2) catalyst.
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S8. Activity of the catalyst after Hot filtration test
0 20 40 60 80 100 120 140 160 180
0
20
40
60
80
100
Con
vers
ion
Time (min)
con. after cat. removed Selectivity of TCV con. after without cat. removed Selectivity of TCV
Fig. S8. Activity of the catalyst after Hot filtration test.
S9: SEM and EDAX images of recycled PCS (α2)
Fig. S9. Scanning electron microscopy (SEM) image of recycled PCS(α2) (A-D) and E show
the SEM-EDAX of the sample. And Table shows the % availability of the elements.
8
S10. 1H and 13C NMR analysis of trans-Carveol1H NMR of trans-Carveol CDCl3 (600 MHz) δ 5.59 (s, 1H), 4.75 (s, 2H), 4.02 (s, 1H), 2.34
(s, 1H), 2.13 (s, 1H), 1.93 (s, 1H), 1.85 (s, 1H), 1.80 (s, 3H), 1.75 (s, 3H), 1.61 (s, 2H)
Fig. S10. 1H NMR of trans-Carveol
13C NMR of trans-Carveol CDCl3 (600 MHz) δ 148.17 (s), 133.29 (s), 124.35 (s), 108.01
(s), 67.52 (s), 35.71 (s), 34.20 (s), 29.98 (s), 28.69 (s), 19.85 (s).
Fig. S11. 13C NMR of trans-Carveol.
0.20.61.01.41.82.22.63.03.43.84.24.65.05.4f1 (ppm)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
2.28
3.19
3.04
1.37
1.08
1.06
1.10
1.02
2.08
1.00
1.26
1.61
1.75
1.80
1.85
1.93
2.13
2.34
4.02
4.75
5.59
CH3
CH3
OHH
H
H2.02.53.03.54.04.55.05.5f1 (ppm)
0.0
0.5
1.0
2.28
3.19
3.04
1.37
1.08
1.06
1.10
1.02
2.08
1.00
1.61
1.75
1.80
1.85
1.93
2.13
2.34
4.02
4.75
5.59
0102030405060708090100110120130140150f1 (ppm)
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
20.9
8
30.9
935
.30
36.8
1
68.7
4
109.
10
125.
44
134.
39
149.
33
CH3
CH3
OHH
H
H
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S11. FTIR spectrum of trans-Carveol.
Fig. S12. Fourier transform infrared spectrum of trans-Carveol.
S12. GC-MS profile of the selected products.
Fig. S13. GC-MS profile for Campholenic aldehyde.
Fig. S14. GC-MS profile for trans-Carveol.
4000 3500 3000 2500 2000 1500 1000 500
% T
rans
mitt
ance
Wavenumber(cm-1)
trans-Carveol
29203341
3083
2727
2342
16441441
1376
1261 1167
1055
962
808
616524672
OO
10
Fig. S15. GC-MS profile for trans-pinocarveol.
Fig. S16. GC-MS profile for trans-Sobrerol.
Fig. S17. GC-MS profile for trans-Pinocarvone.
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