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Supplementary Material Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites Fukun Li, Liam John France, Zhenping Cai, Yingwen Li, Sijie Liu, Hongming Lou, Jinxing Long * , Xuehui Li * School of Chemistry and Chemical Engineering, Pulp & Paper Engineering State Key Laboratory of China, South China University of Technology, Guangzhou, Guangdong, 510640, China * Corresponding author. Tel/Fax: +0086 20 8711 4707; E-mail: [email protected] (X. Li) [email protected] (J. Long). S1

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Supplementary Material

Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over

zirconium phosphates with adjustable Lewis and Brønsted acid sites

Fukun Li, Liam John France, Zhenping Cai, Yingwen Li, Sijie Liu, Hongming Lou, Jinxing

Long*, Xuehui Li*

School of Chemistry and Chemical Engineering, Pulp & Paper Engineering State Key Laboratory

of China, South China University of Technology, Guangzhou, Guangdong, 510640, China

* Corresponding author. Tel/Fax: +0086 20 8711 4707; E-mail: [email protected] (X. Li)

[email protected] (J. Long).

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Scheme S1 The potential applications of GVL.

Figure S1 XRD patterns of as-synthesized zirconium phosphate catalysts.

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Figure S2 NH3-TPD profiles of as-synthesized, used and regenerated zirconium phosphate

catalysts (a) ZrPO-0.50, (b) ZrPO-0.75, (c) ZrPO-1.00, (d) ZrPO-1.25, (e) ZrPO-1.50, (f) ZrPO-

1.75, (g) ZrPO-2.00, (h) ZrPO-1.00 after the first cycle and (i) ZrPO-1.00 after the tenth cycle.

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Table S1 Textural and surface information of as-synthesized, used and regenerated zirconium

phosphate catalysts.

CatalystP/Zr molar

ratio

SBET

(m2 g-1)

Vpore

(cm3 g-1)

Dmean

(nm)

V0.15(N2)d

(cm3 g-1)

V0.15(H2O)e

(cm3 g-1)X0.15

f

ZrPO-0.50 0.88 143.5 0.14 3.9 0.061 0.042 0.70

ZrPO-0.75 1.12 185.0 0.29 6.4 0.075 0.055 0.73

ZrPO-1.00 1.33 248.5 0.58 9.4 0.101 0.078 0.77

ZrPO-1.25 1.56 253.0 0.62 9.8 0.104 0.083 0.80

ZrPO-1.50 1.92 275.5 0.57 8.3 0.114 0.094 0.82

ZrPO-1.75 2.14 275.0 0.56 8.3 0.114 0.096 0.84

ZrPO-2.00 2.38 279.6 0.52 7.4 0.115 0.107 0.93

ZrPO-1.00a 1.33 247.7 0.54 8.7 - - -

ZrPO-1.00b 1.32 217.3 0.43 7.9 - - -

ZrPO-1.00c 1.32 245.3 0.57 9.3 - - -a, b ZrPO-1.00 after the first and tenth cycle respectively. c the regenerated ZrPO-1.00. d Micropore volume calculated from the nitrogen uptake at P/Po=0.15. e the water density at 298 K is 0.997 g cm-1. f X0.15= was measured from the ratio of water vapor uptake volume to nitrogen uptake volume which was obtained at the relative pressure P/Po=0.15

Figure S3 N2 adsorption-desorption isotherms of as-synthesized, used and regenerated zirconium

phosphate catalysts (a) ZrPO-0.50, (b) ZrPO-0.75, (c) ZrPO-1.00, (d) ZrPO-1.25, (e) ZrPO-1.50,

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(f) ZrPO-1.75 and (g) ZrPO-2.00 The inset shows the resulting pore size distribution.

Figure S4 SEM images of as-synthesized zirconium phosphate catalysts (a) ZrPO-0.50, (b) ZrPO-

0.75, (c) ZrPO-1.00, (d) ZrPO-1.25, (e) ZrPO-1.50, (f) ZrPO-1.75 and (g) ZrPO-2.00.

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Figure S5 Water vapor adsorption isotherms of as-synthesized zirconium phosphate catalysts at

298 K.

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Figure S6 XPS spectra of as-synthesized zirconium phosphate (a) survey scan, (b) high resolution

Zr 3d, (c) P 2p and (d) O 1s.

Table S2 Binding energies and surface atomic composition of as-synthesized zirconium phosphate

catalysts determined via XPS.

CatalystBinding energies (eV) Surface compositiona (%)

P/ZrZr 3d3/2 Zr 3d5/2 P 2p O 1s Zr P O

ZrO2 184.4 182.0 - 531.4 530.2 29.9 - 70.0 -

ZrPO-

0.50184.9 182.6 133.5 532.0 530.9 13.8 13.0 73.2

0.93

ZrPO-

0.75185.5 183.2 134.0 532.9 531.6 13.3 13.8 72.8

1.03

ZrPO-

1.00185.6 183.3 134.0 532.6 531.7 11.8 15.1 73.1

1.28

ZrPO-

1.25185.7 183.3 134.1 532.6 531.4 11.0 16.1 72.7

1.46

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ZrPO-

1.50185.9 183.5 134.1 532.9 531.6 10.3 16.8 73.0

1.63

ZrPO-

1.75185.9 183.6 134.1 533.0 531.6 9.7 17.8 72.3

1.84

ZrPO-

2.00186.0 183.7 134.3 533.1 531.8 9.5 18.4 72.2 1.94

a Based on XPS line areas of Zr 3d, P 2p and O 1s.

Table S3 Products detected by GC-MS.

Entry

Retention time (min)

Compound name Structure

1 2.039 n-butanol

2 2.536 isopropyl butyl ether

3 4.033 isopropyl pent-4-enoate

4 4.211 isopropyl pent-2-enoate

5 5.437 isopropyl levulinate

6 5.592isopropyl 4-

isopropoxypentanoate

7 6.587 butyl levulinate

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Figure S7 Effect of reaction temperature and time on BL conversion and product distribution.

Reaction conditions: 2.0 mmol BL, 100 mg ZrPO-1.00, 473 K, 10 mL isopropanol, 1.0 MPa N2.

Signals for i-PP2E, i-PP4E and i-P4(i-P)PA have been magnified 150 times.

Table S4 Reduction potential of hydrogen donors. 1

Entry Hydrogen donor ΔfHº (kJ / mol)[a]

1 Methanol 130.1

2 Ethanol 85.4

3 Isopropanol 70.0

4 2-Butanol 69.3

5 2-Pentanol 67.9a ΔfHº is defined as the difference of the standard molar enthalpy of formation between the alcohol and the corresponding carbonyl compound.

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Figure S8 Conversion of various substrates to GVL at different temperatures in 2 h for (a)

levulinic acid, (b) methyl levulinate, (c) ethyl levulinate, (d) propyl levulinate, (e) isopropyl

levulinate and (f) butyl levulinate. Reaction condition: 2 mmol substrate, 100 mg ZrPO-1.00, 10

mL isopropanol, 2 h, 1 MPa N2.

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Figure S9 Catalyst recycle and regeneration of Zr(OH)4 and ZrPO-1.00 for the transfer

hydrogenation of BL to GVL. Reaction conditions: 2.0 mmol BL, 100 mg catalyst, 10 mL

isopropanol, 483 K, 2.0 h, 1.0 MPa N2.

Figure S10 N2 adsorption-desorption isotherms of the fresh, first cycle, tenth cycle and

regenerated ZrPO-1.00 catalysts. The inset shows pore size distribution.

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Figure S11 High-resolution XPS spectra (a) Zr 3d, (b) P 2p, (c) O 1s of fresh, first and tenth cycle

ZrPO-1.00 catalysts.

Figure S12 Photograph of ZrPO-1.00 catalysts (a) fresh catalyst, (b) the first cycle and (c) the

tenth cycle.

References

[1] J.C. van der Waal, P.J. Kunkeler, K. Tan, H. van Bekkum, J. Catal. 173 (1998) 74-

83.

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