Tailoring interfacial microenvironment of palladium-zeolite catalysts for the efficient low- temperature hydrodeoxygenation of vanillin in water
Item Type Article
Authors Ran, Jiansu;Alfilfil, Lujain;Li, Jingwei;Yangcheng, Ruixue;Liu, Zhaohui;Wang, Qin;Cui, Yuntong;Cao, Tong;Qiao, Min;Yao, Kexin;Zhang, Daliang;Wang, Jianjian
Citation Ran, J., Alfilfil, L., Li, J., Yangcheng, R., Liu, Z., Wang, Q., Cui, Y., Cao, T., Qiao, M., Yao, K., Zhang, D., & Wang, J. (2022). Tailoring interfacial microenvironment of palladium-zeolite catalysts for the efficient low-temperature hydrodeoxygenation of vanillin in water. ChemCatChem. Portico. https://doi.org/10.1002/
cctc.202200397 Eprint version Post-print
DOI 10.1002/cctc.202200397
Publisher Wiley
Journal ChemCatChem
Rights Archived with thanks to ChemCatChem Download date 2023-12-04 19:21:37
Link to Item http://hdl.handle.net/10754/676635
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Supporting Information
Tailoring interfacial microenvironment of palladium-zeolite catalysts for the efficient low-temperature hydrodeoxygenation of vanillin in water
Jiansu Ran,a,b,† Lujain Alfilfil,c,† Jingwei Li,b Ruixue YangCheng,b Zhaohui Liu,b Qin Wang,b Yuntong Cui,b Tong Cao,b Min Qiao,b Kexin Yao,a,b Daliang Zhang,a,b and Jianjian Wanga,b,*
a State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing, 400044, China.
b Multi-scale Porous Materials Center, Institute of Advanced Interdisciplinary Studies & School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400045, China.
c Advanced Membranes and Porous Materials Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
† These authors contributed to this work equally.
* Corresponding author. E-mail address: [email protected] (J. Wang)
Contents
1. Supporting Tables………...2~6
2. Supporting Schemes and Figures………..7~23
3. References………...24~25
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1. Supporting Tables
Table S1. Composition and physical properties of various catalysts.
Entry Samples Si/Ala
BET surface area (m2/g)b
Total pore volume (cm3/g)c
Pd loading (wt.%)d
1 Pd/MS-HZSM-5(30) 34 603 0.55 0.22
2 Pd/MS-HZSM-5(30)e 34 566 0.50 0.21
3 Pd/MS-HZSM-5(50) 45 622 0.64 0.22
4 Pd/MS-HZSM-5(100) 88 653 0.69 0.22
5 Pd/MS-HZSM-5(200) 230 603 0.64 0.22
6 Pd/MS-HZSM-5(300) 274 532 0.57 0.22
7 Pd/Nano-HZSM-5(30) 31 460 0.24 0.21
8 Pd/MS-S-1 - 466 0.60 0.23
a Determined by EDS. b Calculated in the P/P0 range of 0.01 to 0.2. c Collected at P/P0 = 0.92. d Determined by ICP. e Recycled catalyst from 3th Run.
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Table S2. Comparison of catalytic performance for the HDO of VAN in water over various catalysts.
Entry Catalyst
VAN/Pd (mol/mol)
T (℃)
PH2
(MPa)
Time (h)
Conversion (%)
MMP yield
(%) Ref.
1 Pd/C 68 100 3.0 3 > 99 95.0 [1]
2 Pd/CN170 100 100 1.0 1 > 99 52.0 [2]
3 Pd/CN0.132 1000 150 1.0 6 > 99 > 99 [3]
4 Pd/MSMF 200 100 2.0 1 > 99 67.8 [4]
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Pd/SO3H-MIL-
101(Cr) 1000 100 0.5 5 > 99 96.1 [5]
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Pd@MIL-101(
Cr) 35 100 0.2 2 86.4 70.9 [6]
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Pd@NH2-UiO-
66 212 100 0.5 1 > 99 > 99 [7]
8
Pd@UiO-66(Hf
) 83 90 0.3 2 > 99 > 99 [8]
9 Pd/γ-Al2O3 350 90 1.0 1 95.0 65.6 [3]
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Pd/MS-HZSM-
5(30) 1200 60 2 5 > 99 94.7 This work
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Pd/Nano-HZS
M-5(30) 1200 60 2 5 > 99 77.6 This work
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Table S3. HDO of VAN over Pd/MS-HZSM-5(30) under various reaction conditions.
Entry
VAN/Pd (mol/mol)
Temperature (℃)
H2 pressure (MPa)
Time (h)
Conversion (%)
VAL yield (%)
MMP yield (%)
1 1200 60 1 5 98.9 15.6 71.8
2 1200 60 2 5 > 99 0.7 94.7
3 1200 60 3 5 > 99 3.6 89.7
4 1200 80 2 5 > 99 0.0 94.1
5 600 60 2 5 > 99 0.0 95.8
6 600 80 2 5 > 99 0.0 95.5
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Table S4. The influence of distribution of Pd particle size towards its catalytic performance in the HDO of VAN.a
Entry Samples
Pd size (nm)b
Pd dispersion (%)c
Conversion (%)
VAL yield (%)
MMP yield (%)
1 Pd/MS-HZSM-5(30) 1.5 21.6 > 99 0.7 94.7
2 Pd/MS-HZSM-5(30)-T1 2.6 18.7 > 99 9.9 79.6
3 Pd/MS-HZSM-5(30)-T2 3.2 17.1 > 99 15.7 71.3
a Reaction conditions: VAN/Pd = 1200 (mol/mol), 10 mL of water, 60 ℃, 5 h, and 2 MPa of H2. b Measured by statistical result from TEM images. c Calculated according to CO uptake.
6 Table S5. HDO of VAN over different catalysts.a
Entry Samples Conversion (%) VAL yield (%) MMP yield (%)
1 Blankb 3.6 0.3 0
2 MS-HZSM-5(30) 4.0 0.0 0
3 MS-S-1 7.5 0.0 0
4 Pd/MS-S-1+MS-HZSM-5(30)c 99.2 30.5 46.9
5 Pd/MS-HZSM-5(30) 100 0.7 94.7
6 Pd/MS-HZSM-5(30)d 100 48.3 7.8
7 Pd/MS-HZSM-5(30)e 100 36.7 31.2
8 Pd/MS-HZSM-5(30)f 100 33.4 44.1
9 Pd/MS-HZSM-5(30)g 100 20.9 62.8
a Reaction conditions: VAN/Pd = 1200 (mol/mol), 10 mL of water, 60 ℃, 5 h, and 2 MPa of H2. b Without catalyst. c Pd/MS-S-1 and MS-HZSM-5(30) was physically mixed. d Pd/MS-HZSM-5(30) was treated with pyridine. e Pyridine-adsorbed Pd/MS-HZSM-5(30) was treated in H2 at 400 ℃ for 4 h. f Pd/MS-HZSM-5(30) was treated with 2,6-di-tert-butylpyridine (DTBP). g DTBP-adsorbed Pd/MS-HZSM-5(30) was treated in H2 at 400 ℃ for 4 h.
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2. Supporting Schemes and Figures
Scheme S1. Reaction pathways for the hydrodeoxygenation (HDO) of VAN to MMP.
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Fig. S1. (A) HRTEM and (B) HAADF-STEM images of Pd/MS-HZSM-5(30).
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Fig. S2. Two typical GC chromatography records of HDO of VAN over (A) Pd/MS-HZSM-5(30) and (B) Pd/MS-S-1, where the value of vertical axis was kept in the same range.
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Fig. S3. Reusability of Pd/MS-HZSM-5(30). Catalyst was collected from 3th Run, washed with ethanol thrice, calcined at 550 ℃ for 4 h in air, reduced at 200 ℃ for 2 h, and then used in 4th Run. Reaction conditions:
VAN/Pd = 1200 (mol/mol), 10 mL of water, 60 ℃, 5 h, and 2 MPa of H2.
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Fig. S4. TG curves of fresh (a) Pd/MS-HZSM-5(30) and (b) recycled Pd/MS-HZSM-5(30)-Run3th. The recycled Pd/MS-HZSM-5(30)-Run3th was directly collected from 3th Run without treatment of calcination and reduction.
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Fig. S5. Hot filtration test for Pd/MS-HZSM-5(30): (A) VAN conversion, (B) VAL yield, and (C) MMP yield.
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Fig. S6. XRD patterns of (a) fresh Pd/MS-HZSM-5(30) and (b) recycled Pd/MS-HZSM-5(30)-Run4th. The recycled Pd/MS-HZSM-5(30)-Run4th was collected from 4th Run, washed with ethanol thrice, calcined at 550 ℃ for 4 h in air, and reduced at 200 ℃ for 2 h.
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Fig. S7. Nitrogen isotherms of (a) fresh Pd/MS-HZSM-5(30) and (b) recycled Pd/MS-HZSM-5(30)-Run4th. The recycled Pd/MS-HZSM-5(30)-Run4th was collected from 4th Run, washed with ethanol thrice, calcined at 550 ℃ for 4 h in air, and reduced at 200 ℃ for 2 h.
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Fig. S8. (A) TEM image and (B) the distribution of Pd nanoparticle size of recycled Pd/MS-HZSM-5(30)-Run4th. The recycled Pd/MS-HZSM-5(30)-Run4th was collected from 4th Run, washed with ethanol thrice, calcined at 550 ℃ for 4 h in air, and reduced at 200 ℃ for 2 h.
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Fig. S9. XRD patterns of (a) Pd/MS-HZSM-5(30), (b) Pd/MS-HZSM-5(30)-T1, and (c) Pd/MS-HZSM-5(30)-T2.
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Fig. S10. NH3-TPD curves of (A) Pd/MS-HZSM-5(30) and (B) Pd/Nano-HZSM-5(30) catalysts.
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Fig. S11. XRD patterns of (a) Pd/MS-HZSM-5(30), (b) Pd/MS-HZSM-5(50), (c) Pd/MS-HZSM-5(100), (d) Pd/MS-HZSM-5(200), and (e) Pd/MS-HZSM-5(300).
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Fig. S12. N2 isotherms of (a) Pd/MS-HZSM-5(30), (b) Pd/MS-HZSM-5(50), (c) Pd/MS-HZSM-5(100), (d) Pd/MS-HZSM-5(200), and (e) Pd/MS-HZSM-5(300). Isotherms of b-e were moved vertically for easy comparison.
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Fig. S13. Catalytic performances for HDO of VAN over (a) Pd/MS-HZSM-5(30), (b) Pd/MS-HZSM-5(50), (c) Pd/MS-HZSM-5(100), (d) Pd/MS-HZSM-5(200), and (e) Pd/MS-HZSM-5(300). Reaction conditions: VAN/Pd = 1200 (mol/mol), 10 mL of water, 60 ℃, 5 h, and 2 MPa of H2.
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Fig. S14. HDO of VAN to MMP over Pd/MS-HZSM-5 with various ratios of Si to Al, where total BAS amount was calculated based on the actual percentage of Al in the zeolite measured by EDS. The dash line was given as guidance. Reaction conditions: VAN/Pd = 1200 (mol/mol), 10 mL of water, 60 ℃, 5 h, and 2 MPa of H2.
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Fig. S15. FTIR spectra of VAN-adsorbed (A) Pd/MS-HZSM-5(30) and (B) Pd/MS-S-1 treated at different
conditions. Pure catalyst represented catalyst without adsorption of VAN. FTIR spectra were recorded from catalyst which was pre-treated at different temperatures in a flow of H2. Mass of Pd/MS-HZSM-5(30) and Pd/MS-S-1 was identical used in the FTIR test. Dash line at 1714 cm-1 was assigned to the C=O stretching vibration of the aldehyde group, and it around 1740 cm-1, probably represented activated aldehyde groups adsorbed onto catalyst surface or was attributed to the conjugation effect of vibrations of C=C.
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Fig. S16. FTIR spectra of VAL-adsorbed (A) Pd/MS-HZSM-5(30) and (B) Pd/MS-S-1 treated at different
conditions. Pure catalyst represented catalyst without adsorption of VAL. FTIR spectra were recorded from catalyst which was pre-treated at different temperatures in a flow of H2. Mass of Pd/MS-HZSM-5(30) and Pd/MS-S-1 was identical used in the FTIR test. Dash lines at 1515, 1466, 1452, and 1379 cm-1 were attributed to ν(benzene ring), ν(CH3O), ν1(CH3), and v2(CH3), respectively.
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3. References
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