Citation: GAO Jia, SONG Fujiao, CHENG Wenqiang, GE Yan, XU Qi. Catalytic Performance of Pd-Cu/ZrO₂ Catalyst for Hydrogenation of Carbon Dioxide to Methanol[J]. Chinese Journal of Applied Chemistry, ;2020, 37(2): 160-167. doi: 10.11944/j.issn.1000-0518.2020.02.190211 shu

Catalytic Performance of Pd-Cu/ZrO₂ Catalyst for Hydrogenation of Carbon Dioxide to Methanol

GAO Jia ^a ,
SONG Fujiao ^b ,
CHENG Wenqiang ^c ,
GE Yan ^c ,
XU Qi ^a,,

a.
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China
b.
School of Environmental Science Engineering, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, China
c.
School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, China

Corresponding author: XU Qi, ycxqsteve@163.com
Received Date: 31 July 2019
Revised Date: 30 September 2019
Accepted Date: 4 November 2019

Fund Project: the National Natural Science Foundation of China 21802119Supported by the National Natural Science Foundation of China(No.21802119)

Figures(6)

Cu/ZrO₂ catalysts with the Cu/Zr molar ratio of 1:1, 1:2, 1:4 and 1:8 were prepared by the sol-gel method. When n(Cu):n(Zr)=1:4, a high CO₂ conversion (8.0%) with methanol selectivity of 59.5% was achieved. To increase CO₂ conversion and CH₃OH selectivity, Pd-Cu/ZrO₂ catalyst with the Cu/Zr molar ratio of 1:4 and 1% mass fraction of Pd was synthesized by the impregnation method. The results showed that CO₂ conversion and CH₃OH yield over the Pd-Cu/ZrO₂ catalyst were 40.0% and 80.9% higher than that over the Cu/ZrO₂ catalyst at 250℃, 2 MPa, 12000 mL/(g·h) and V(H₂):V(CO₂)=3:1. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy analysis (FT-IR), N₂ adsorption-desorption (BET), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction of H₂(H₂-TPR) results indicated that addition of Pd improved the dispersion and surface area of the catalyst. The strong interaction between Pd and Cu species leads to the shift of Cu2p to low binding energies and decreases the catalyst reduction temperature, which exhibits high catalytic performance for hydrogenation of CO₂.
- sol-gel method,
- impregnation method,
- carbon dioxide hydrogenation,
- methanol
1. [1]
  Bao J, Yang G H, Yoneyama Y. Significant Advances in C1 Catalysis:Highly Efficient Catalysts and Catalytic Reactions[J]. ACS Catal, 2019,9(4):3026-3053. doi: 10.1021/acscatal.8b03924
2. [2]
  DING Fanshu, NIE Xiaowa, LIU Min. Research Progress in Catalytic Conversion of Carbon Dioxide to C₂+Hydrocarbons over Fe-Based Catalysts[J]. Chinese J Appl Chem, 2016,33(2):123-132.
3. [3]
  LI Qingxun, WANG Zongbao, LOU Shujie. Research Progress in Methanol Production from Carbon Dioxide Hydrogenation[J]. Mod Chem Ind, 2019,39(5):19-23.
4. [4]
  Cassone G, Pietrucci F, Saija F. One-Step Electric-Field Driven Methane and Formaldehyde Synthesis from Liquid Methanol[J]. Chem Sci, 2017,8(3):2329-2336. doi: 10.1039/C6SC04269D
5. [5]
  Qian Q L, Zhang J J, Cui M. Synthesis of Acetic Acid via Methanol Hydrocarboxylation with CO₂ and H₂[J]. Nat Commun, 2016,711481. doi: 10.1038/ncomms11481
6. [6]
  Chu Z, Chen H B, Yu Y. Surfactant-Assisted Preparation of Cu/ZnO/Al₂O₃ Catalyst for Methanol Synthesis from Syngas[J]. J Mol Catal A-Chem, 2013,366:48-53. doi: 10.1016/j.molcata.2012.09.007
7. [7]
  Wu J G, Saito M, Takeuchi M. The Stability of Cu/ZnO-Based Catalysts in Methanol Synthesis from a CO₂-Rich Feed and from a CO-Rich Feed[J]. Appl Catal A-Gen, 2001,218(1/2):235-240.
8. [8]
  ZUO Yizan, ZHANG Qiang, HAN Minghan. The Sintering of a Cu-Based Methanol Synthesis Catalyst[J]. Chinese J Catal, 2009,30(7):624-630. doi: 10.3321/j.issn:0253-9837.2009.07.008
9. [9]
  Oliver M, Antonio J M, Cecilia M. Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO₂ Hydrogenation[J]. Angew Chem Int Ed, 2016,55(21):6261-6265. doi: 10.1002/anie.201600943
10. [10]
  Samson K, Sliwa M, Socha R P. Influence of ZrO₂ Structure and Copper Electronic State on Activity of Cu/ZrO₂ Catalysts in Methanol Synthesis from CO₂[J]. ACS Catal, 2014,4(10):3730-3741. doi: 10.1021/cs500979c
11. [11]
  Yao L B, Shen X C, Pan Y B. Synergy Between Active Sites of Cu-In-Zr-O Catalyst in CO₂ Hydrogenation to Methanol[J]. J Catal, 2019,372:74-85. doi: 10.1016/j.jcat.2019.02.021
12. [12]
  Chen D W, Mao D S, Xiao J. CO₂ Hydrogenation to Methanol over CuO-ZnO-TiO₂-ZrO₂:A Comparison of Catalysts Prepared by Sol-Gel, Solid-State Reaction and Solution-Combustion[J]. J Sol-Gel Sci Technol, 2018,86(3):719-730. doi: 10.1007/s10971-018-4680-4
13. [13]
  Li L, Mao D S, Yu J. Highly Selective Hydrogenation of CO₂ to Methanol over CuO-ZnO-ZrO₂ Catalysts Prepared by a Surfactant-Assisted Co-precipitation Method[J]. J Power Sources, 2015,279(1):394-404.
14. [14]
  JIA Ruokun, ZHAO Guangyu, LIN Songzhu. Preparation of CuO-ZnO/Al₂O₃ Catalysts by Azeotropic Distillation Method and Its Influence on the Catalytic Performance[J]. Chinese J Appl Chem, 2015,32(5):570-575.
15. [15]
  Witoon T, Chalorngtham J, Dumrongbunditkul P. CO₂ Hydrogenation to Methanol over Cu/ZrO₂ Catalysts: Effects of Zirconia Phases[J]. Chem Eng J, 2016,293:327-336. doi: 10.1016/j.cej.2016.02.069
16. [16]
  Chang K, Wang T F, Chen J G. Hydrogenation of CO₂ to Methanol over CuCeTiO_x Catalysts[J]. Appl Catal B-Environ, 2017,206:704-711. doi: 10.1016/j.apcatb.2017.01.076
17. [17]
  Azenha C S R, Mateos-Pedrero C, Queir s S. Innovative ZrO₂-supported CuPd Catalysts for the Selective Production of Hydrogen from Methanol Steam Reforming[J]. Appl Catal B-Environ, 2017,203:400-407. doi: 10.1016/j.apcatb.2016.10.041
18. [18]
  Zhang Y, Ye C L, Guo C L. In₂O₃-Modified Cu/SiO₂ as an Active and Stable Catalyst for the Hydrogenation of Methyl Acetate to Ethanol[J]. Chinese J Catal, 2018,39(1):99-108. doi: 10.1016/S1872-2067(17)62932-2
19. [19]
  Xu J H, Su X, Liu X Y. Methanol Synthesis from CO₂ and H₂ over Pd/ZnO/Al₂O₃:Catalyst Structure Dependence of Methanol Selectivity[J]. Appl Catal A-Gen, 2016,514:51-59. doi: 10.1016/j.apcata.2016.01.006
20. [20]
  YU Jintao, CAO Jingshun, WEI Yongmei. Modification of Cu/SBA-15 Catalyst And Hydrogenation of Esters Catalyzed with the Same[J]. Petrochem Technol, 2019,48(6):531-538. doi: 10.3969/j.issn.1000-8144.2019.06.001
21. [21]
  Zhu J J, Ma L R, Feng J. Facile Synthesis of Cu Nanoparticles on Different Morphology ZrO₂ Supports for Catalytic Hydrogen Generation from Ammonia Borane[J]. J Mater Sci-Mater Electron, 2018,29(17):14971-14980. doi: 10.1007/s10854-018-9635-6
22. [22]
  CHEN Lin. On the Gas-Phase Catalytic Hydrodechlorination of Chlorobenzene and 1, 2-Dichloroethane over Supported Catalysts[D]. Nanjing: Nanjing University, 2014(in Chinese).
23. [23]
  Witoon T, Kidkhunthod P, Chareonpanich M. Direct Synthesis of Dimethyl Ether from CO₂ and H₂ over Novel Bifunctional Catalysts Containing CuO-ZnO-ZrO₂ Catalyst Admixed with WO_x/ZrO₂ Catalysts[J]. Chem Eng J, 2018,348:713-722. doi: 10.1016/j.cej.2018.05.057
24. [24]
  Cheng J, Xuan X X, Yang X. Selective Reduction of CO₂ to Alcohol Products on Octahedral Catalyst of Carbonized Cu (BTC) Doped with Pd Nanoparticles in a Photoelectrochemical Cell[J]. Chem Eng J, 2019,358:860-868. doi: 10.1016/j.cej.2018.10.091
25. [25]
  Din I U, Shaharunb M S, Naeem A. Carbon Nanofibers Based Copper/Zirconia Catalysts for Carbon Dioxide Hydrogenation to Methanol:Effect of Copper Concentration[J]. Chem Eng J, 2018,334:619-629. doi: 10.1016/j.cej.2017.10.087
26. [26]
  Zhu H W, Razzaq R, Li C S. Catalytic Methanation of Carbon Dioxide by Active Oxygen Material Ce_xZr_1-xO₂ Supported Ni Co Bimetallic Nanocatalysts[J]. AIChE J, 2013,59(7):2567-2576. doi: 10.1002/aic.14026
27. [27]
  Shi Z S, Tan Q Q, Wu D F. Ternary Copper Cerium Zirconium Mixed Metal Oxide Catalyst for Direct CO₂ Hydrogenation to Methanol[J]. Mater Chem Phys, 2018,219:263-272. doi: 10.1016/j.matchemphys.2018.08.038
28. [28]
  Andrés G T, Anna R, Edward R W. PdIn Intermetallic Nanoparticles for the Hydrogenation of CO₂ to Methanol[J]. Appl Catal B-Environ, 2018,220:9-18. doi: 10.1016/j.apcatb.2017.07.069
29. [29]
  Wang G, Mao D S, Guo X M. Enhanced Performance of the CuO-ZnO-ZrO₂ Catalyst for CO₂ Hydrogenation to Methanol by WO₃ Modification[J]. Appl Surf Sci, 2018,456:403-409. doi: 10.1016/j.apsusc.2018.06.090
30. [30]
  Dasireddy V D B C, Neja S Š, Blaž L. Correlation Between Synthesis pH, Structure and Cu/MgO/Al₂O₃ Heterogeneous Catalyst Activity and Selectivity in CO₂ Hydrogenation to Methanol[J]. J CO₂ Util, 2018,28:189-199. doi: 10.1016/j.jcou.2018.09.002
31. [31]
  Ben S G, Yuan F L, Zhu Y J. Effect of Zr Addition on Catalytic Performance of Cu-Zn-Al Oxides for CO₂ Hydrogenation to Methanol[J]. Chem Res Chinese Uinv, 2016,32(6):1005-1009. doi: 10.1007/s40242-016-6130-6
32. [32]
  Ezeh C I, Yang X G, He J. Correlating Ultrasonic Impulse and Addition of ZnO Promoter with CO₂ Conversion and Methanol Selectivity of CuO/ZrO₂ Catalysts[J]. Ultrason Sonochem, 2018,42:48-56. doi: 10.1016/j.ultsonch.2017.11.013
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沈阳化工大学材料科学与工程学院沈阳 110142

Catalytic Performance of Pd-Cu/ZrO2 Catalyst for Hydrogenation of Carbon Dioxide to Methanol

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通讯作者: 陈斌, bchen63@163.com

Catalytic Performance of Pd-Cu/ZrO₂ Catalyst for Hydrogenation of Carbon Dioxide to Methanol