Citation: Ying Liu, Xiaofang Liu, Lin Xia, Chaojie Huang, Zhaoxuan Wu, Hui Wang, Yuhan Sun. Methanol Synthesis by CO_x Hydrogenation over Cu/ZnO/Al₂O₃ Catalyst via Hydrotalcite-Like Precursors: the Role of CO in the Reactant Mixture[J]. Acta Physico-Chimica Sinica, ;2022, 38(3): 200201. doi: 10.3866/PKU.WHXB202002017 shu

Methanol Synthesis by CO_x Hydrogenation over Cu/ZnO/Al₂O₃ Catalyst via Hydrotalcite-Like Precursors: the Role of CO in the Reactant Mixture

Ying Liu ^{1, 2} ,
Xiaofang Liu ¹ ,
Lin Xia ¹ ,
Chaojie Huang ^{1, 2} ,
Zhaoxuan Wu ¹ ,
Hui Wang ^{1, 2,,} ,
Yuhan Sun ^{1, 2, 3,,}

1.
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
School of Physical Science and Technology, Shanghai Tech University, Shanghai 201203, China

Corresponding author: Hui Wang, wanghh@sari.ac.cn Yuhan Sun, sunyh@sari.ac.cn
Received Date: 17 February 2020
Revised Date: 13 March 2020
Accepted Date: 27 March 2020
Available Online: 31 March 2020
Fund Project: the National Natural Science Foundation of China 21776296the National Natural Science Foundation of China 21905291National Key Research and Development Program of China 2017YFB0602203Strategic Priority Research Program of the Chinese Academy of Sciences XDA21090201the Chinese Academy of Sciences ZDRW-ZS-2018-1-3the Shanghai Sailing Program, China 19YF1453000

Catalytic hydrogenation of CO₂ to methanol has attracted considerable attention due to its potential in alleviating global warming and mitigating the dependence on fossil fuels. Cu-based catalysts are widely used in industry because of their high activity for methanol production. However, the reaction still suffers from low methanol selectivity because of the generation of CO as a by-product via the reverse water gas shift reaction (RWGS). The formation of another by-product H₂O leads to inevitable Cu sintering, which decreases the methanol production rate. It is well known that CO can alter competitive molecular adsorption on the surface and the redox behavior of the active sites; hence, CO doping in feed gas might not only inhibit the RWGS but also minimize surface poisoning by the adsorbed oxygen. On the other hand, CO₂ hydrogenation to methanol over Cu-based catalysts is a structure-sensitive reaction, and a change in the precursor can have a remarkable influence on the structure and morphology of the catalyst, and ultimately, the catalytic performance. In this work, Cu/ZnO/Al₂O₃ catalysts have been prepared via a hydrotalcite-like precursor (CHT-CZA) and a complex phase precursor (CNP-CZA) using co-precipitation and ammonia evaporation methods. Subsequently, the performance of the two types of catalysts with different CO contents (CO₂: CO:H₂:N₂ = x:(24.5 - x):72.5:3) is compared at 250 ℃ and 5 MPa in order to explore the role of CO. The evaluation results show that both catalysts follow a similar trend in the conversion of CO and CO₂ as well as the space-time-yield (STY) of MeOH and H₂O. The conversions of CO₂ and STY_H₂O decrease gradually with an increase in the CO volume, but STY_MeOH is positively correlated with the CO volume. Furthermore, X-ray photoelectron spectroscopy (XPS) analysis reveals that the amount of reduced Cu species on the surface increases with increasing CO content. Judging from these results, the introduction of CO inhibits the RWGS and enhances the methanol yield for both catalysts by removing the surface oxygen as the reducing agent and thereby facilitating the exposure of the active reduced Cu species. On the other hand, transmission electron microscopy (TEM) observations indicate the doped CO may cause agglomeration of particles due to over-reduction, leading to gradual catalyst deactivation. Compared with the traditional CNP-CZA, the catalyst derived from hydrotalcite-like compounds exhibits better activity and long-term stability under all atmospheres, at different CO doping levels. This is because the hydrotalcite-like layer structure helps maintain the active metal state and confine the structure by limiting the agglomeration of Cu species.
- CO₂ hydrogenation,
- Methanol synthesis,
- Cu/ZnO/Al₂O₃ catalyst,
- CO doping,
- Hydrotalcite-like precursors
1. [1]
  Song, C. S. Catal. Today 2017, 115, 2. doi: 10.1016/j.cattod.2006.02.029 doi: 10.1016/j.cattod.2006.02.029
2. [2]
  Aas, N.; Li, Y. X.; Bowker, M. Phys. Condes. Matter 1991, 3, S281. doi: 10.1088/0953-8984/3/S/044 doi: 10.1088/0953-8984/3/S/044
3. [3]
  Choi, E. J.; Lee, Y. H.; Lee, D. W.; Moon, D. J.; Lee, K. Y. Mol. Catal. 2017, 434, 146. doi: 10.1016/j.mcat.2017.02.005 doi: 10.1016/j.mcat.2017.02.005
4. [4]
  Ortelli, E. E.; Wambach. J.; Wokaun, A. Appl. Catal. A: Gen. 2001, 216, 227. doi: 10.1016/s0926-860x(01)00569-5 doi: 10.1016/s0926-860x(01)00569-5
5. [5]
  Liu, X. M; Lu, G. Q. Ind. Eng. Chem. Res. 2003, 42, 6518. doi: 10.1021/ie020979s doi: 10.1021/ie020979s
6. [6]
  Olah, G, A. Appl. Catal. A: Gen. 2005, 44, 2636. doi: 10.1002/anie.200462121 doi: 10.1002/anie.200462121
7. [7]
  Melián-Cabrera, I.; Granados, M. L.; Fierro, J. L. G. Catal. Lett. 2002, 79, 165. doi: 10.1023/A:1015316610657 doi: 10.1023/A:1015316610657
8. [8]
  Jadhav, S. G.; Vaidya, P. D.; Bhanage, B. M.; Joshi, J. B. Chem. Eng. Res. Des. 2014, 92, 2557. doi: 10.1016/j.cherd.2014.03.005 doi: 10.1016/j.cherd.2014.03.005
9. [9]
  Gao, P.; Li, F.; Xiao, F. K.; Zhao, N.; Sun, N. N.; Wei, W.; Zhong, L. S.; Sun, Y. H. Catal. Sci. Technol. 2012, 2, 1447. doi: 10.1039/C2CY00481J doi: 10.1039/C2CY00481J
10. [10]
  Alejandre, A.; Medina, F.; Rodriguez, X.; Salagre, P.; Sueiras, J. E. J. Catal. 1999, 188, 311. doi: 10.1006/jcat.1999.2625 doi: 10.1006/jcat.1999.2625
11. [11]
  Bhattacharyya, A.; Chang, V. W.; Schumacher, D. J. Appl. Clay Sci. 1998, 13, 317. doi: 10.1016/S0169-1317(98)00030-1 doi: 10.1016/S0169-1317(98)00030-1
12. [12]
  Cavani, F.; Trifiro, F.; Vaccari, A. Catal. Today 1991, 11, 173. doi: 10.1016/0920-5861(91)80068-K doi: 10.1016/0920-5861(91)80068-K
13. [13]
  Climent, M. J.; Corma, A.; Iborra, S.; Primo, J. J. Catal. 1995, 151, 60. doi: 10.1006/jcat.1995.1008 doi: 10.1006/jcat.1995.1008
14. [14]
  Constantino, V. R. L.; Pinnavaia, T. J. Inorg. Chem. 1995, 34, 883. doi: 10.1021/ic00108a020 doi: 10.1021/ic00108a020
15. [15]
  Corma, A.; Fornes, V.; Martinaranda, R. M.; Rey, F. J. Catal. 1992, 134, 58. doi: 10.1016/0021-9517(92)90209-Z doi: 10.1016/0021-9517(92)90209-Z
16. [16]
  Fornasari, G.; Gazzano, M.; Matteuzzi, D.; Trifiro, F. Appl. Clay Sci. 1995, 10, 69. doi: 10.1016/0169-1317(95)00022-V doi: 10.1016/0169-1317(95)00022-V
17. [17]
  Gao, P.; Li, F.; Zhao, N.; Wang, H.; Wei, W.; Sun, Y. H. Acta Phys. -Chim. Sin. 2014, 30, 1155. doi: 10.3866/PKU.WHXB201401252
18. [18]
  Gao, P.; Li, F.; Xiao, F. K.; Zhao, N.; Wei, W.; Zhong, L. S.; Sun, Y. H. Catal. Today 2012, 194, 9. doi: 10.1016/j.cattod.2012.06.012 doi: 10.1016/j.cattod.2012.06.012
19. [19]
  Gao, P.; Li, F.; Zhan, H. J.; Zhao, N.; Xiao, F. K.; Wei, W.; Zhong, L. S.; Wang, H.; Sun, Y. H. J. Catal. 2013, 298, 51. doi: 10.1016/j.jcat.2012.10.030 doi: 10.1016/j.jcat.2012.10.030
20. [20]
  Gao, P.; Li, F.; Zhan, H. J.; Zhao, N.; Xiao, F. K.; Wei, W.; Zhong, L. S.; Sun, Y. H. Catal. Commun. 2014, 50, 78. doi: 10.1016/j.catcom.2014.03.006 doi: 10.1016/j.catcom.2014.03.006
21. [21]
  Gao, P.; Li, F.; Zhao, N.; Xiao, F. K.; Wei, W.; Zhong, L. S.; Sun, Y. H. Appl. Catal. A: Gen. 2013, 468, 442. doi: 10.1016/j.apcata.2013.09.026 doi: 10.1016/j.apcata.2013.09.026
22. [22]
  Gao, P.; Zhong, L. S.; Zhang, L. N.; Wang, H.; Zhao, N.; Wei, W.; Sun, Y. H. Catal. Sci. Technol. 2015, 5, 4365. doi: 10.1039/C5CY00372E doi: 10.1039/C5CY00372E
23. [23]
  Sahibzada, M.; Metcalfe, I. S.; Chadwick, D. J. Catal. 1998, 174, 111. doi: 10.1006/jcat.1998.1964 doi: 10.1006/jcat.1998.1964
24. [24]
  Lee, J. S.; Lee, K. H.; Lee, S. Y. J. Catal. 1993, 144, 414. doi: 10.1006/jcat.1993.1342 doi: 10.1006/jcat.1993.1342
25. [25]
  Yuan, Z.; Wang, L.; Wang, J.; Xia, S.; Chen, P.; Hou, Z.; Zheng, X. Appl. Catal. B: Environ. 2011, 101, 431. doi: 10.1016/j.apcatb.2010.10.013 doi: 10.1016/j.apcatb.2010.10.013
26. [26]
  Evans, J. W.; Wainwright, M. S.; Bridgewater, A. J.; Young, D. J. Appl. Catal. 1983, 7, 75. doi:10.1016/0166-9834(83)80239-5 doi: 10.1016/0166-9834(83)80239-5
27. [27]
  Cheng, J.; Wang, X.; Yu, J.; Hao, Z.; Xu, Z. P. J. Phys. Chem. C 2011, 115, 6651. doi: 10.1021/jp112031e doi: 10.1021/jp112031e
28. [28]
  Xiao, S.; Zhang, Y. F.; Gao, P.; Zhong, L. S.; Li, X. P.; Zhang, Z. Z.; Wang, H.; Wei, W.; Sun, Y. H. Catal. Today 2017, 281, 327. doi: 10.1016/j.cattod.2016.02.004 doi: 10.1016/j.cattod.2016.02.004
29. [29]
  Liao, P. Y.; Zhang, C.; Zhang, L. J.; Yang, Y. Z.; Zhong, L. S.; Guo, X. Y.; Wang, H.; Sun, Y. H. Acta Phys. -Chim. Sin. 2017, 33, 1672. doi: 10.3866/PKU.WHXB201704143
30. [30]
  Velu, S.; Sabde, D. P.; Shah, N.; Sivasanker, S. Chem. Mater. 1998, 10, 3451. doi: 10.1021/cm980185x doi: 10.1021/cm980185x
31. [31]
  Zhang, C.; Yang, H. Y.; Gao, P.; Zhu, H.; Zhong, L. S.; Wang, H.; Wei, W.; Sun, Y. H. J. CO₂ Util. 2017, 17, 263. doi: 10.1016/j.jcou.2016.11.015 doi: 10.1016/j.jcou.2016.11.015
32. [32]
  Guo, X.; Mao, D.; Lu, G.; Wang, S.; Wu, G. J. Catal. 2010, 271, 178. doi: 10.1016/j.jcat.2010.01.009 doi: 10.1016/j.jcat.2010.01.009
33. [33]
  Zhang, L. H.; Li, F.; Evans, D. G.; Duan, X. Mater. Chem. Phys. 2004, 87, 402. doi: 10.1016/j.matchemphys.2004.06.010 doi: 10.1016/j.matchemphys.2004.06.010
34. [34]
  Kuhl, S.; Tarasov, A.; Zander, S.; Kasatkin, I.; Behrens, M. Chem. Eur. J. 2014, 20, 3782. doi: 10.1002/chem.201302599 doi: 10.1002/chem.201302599
35. [35]
  Wu, G. D.; Wang, X. L.; Wei, W.; Sun, Y. H. Appl. Catal. A: Gen. 2010, 377, 107. doi: 10.1016/j.apcata.2010.01.023 doi: 10.1016/j.apcata.2010.01.023
36. [36]
  Di Cosimo, J. I.; Diez, V. K.; Xu, M.; Iglesia, E.; Apesteguia, C. R. J. Catal. 1998, 178, 499. doi: 10.1006/jcat.1998.2161 doi: 10.1006/jcat.1998.2161
37. [37]
  Klier, K.; Chatikavanij, V.; Herman, R. G.; Simmons, G. W. J. Catal. 1982, 74, 343. doi: 10.1016/0021-9517(82)90040-9 doi: 10.1016/0021-9517(82)90040-9
38. [38]
  Burch, R.; Golunski, S. E.; Spencer, M. S. Catal. Lett. 1990, 5, 55. doi: 10.1007/BF00772093 doi: 10.1007/BF00772093
39. [39]
  Fujitani, T.; Saito, M.; Kanai, Y.; Kakumoto, T.; Watanabe, T.; Nakamura, J.; Uchijima, T. Catal. Lett. 1994, 25, 271. doi: 10.1007/BF00816307 doi: 10.1007/BF00816307
40. [40]
  Yang, C.; Ma, Z.Y.; Zhao, N.; Wei, W.; Hu, T. D.; Sun, Y. H. Catal. Today 2006, 115, 222. doi: 10.1016/j.cattod.2006.02.077 doi: 10.1016/j.cattod.2006.02.077
41. [41]
  Chinchen, G. C.; Denny, P. J.; Parker, D. G.; Spencer, M. S.; Whan, D. A. Appl. Catal. 1987, 30, 333. doi: 10.1016/S0166-9834(00)84123-8 doi: 10.1016/S0166-9834(00)84123-8
42. [42]
  Chinchen, G. C.; Waugh, K. C. J. Catal. 1986, 97, 280. doi: 10.1016/0021-9517(86)90063-1 doi: 10.1016/0021-9517(86)90063-1
43. [43]
  Chinchen, G. C.; Waugh, K. C.; Whan, D. A. Appl. Catal. 1986, 25, 101. doi: 10.1016/S0166-9834(00)81226-9 doi: 10.1016/S0166-9834(00)81226-9
44. [44]
  Sun, J. T.; Metcalfe, I. S.; Sahibzada, M. Ind. Eng. Chem. Res. 1999, 38, 3868. doi: 10.1021/ie990078s doi: 10.1021/ie990078s
1. [1]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
2. [2]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
3. [3]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
4. [4]
  Qian-Qian Tang , Li-Fang Feng , Zhi-Peng Li , Shi-Hao Wu , Long-Shuai Zhang , Qing Sun , Mei-Feng Wu , Jian-Ping Zou . Single-atom sites regulation by the second-shell doping for efficient electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(9): 109454-. doi: 10.1016/j.cclet.2023.109454
5. [5]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
6. [6]
  Liang Ma , Zhou Li , Zhiqiang Jiang , Xiaofeng Wu , Shixin Chang , Sónia A. C. Carabineiro , Kangle Lv . Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100416-100416. doi: 10.1016/j.cjsc.2023.100416
7. [7]
  Shu-Ran Xu , Fang-Xing Xiao . Metal halide perovskites quantum dots: Synthesis, and modification strategies for solar CO2 conversion. Chinese Journal of Structural Chemistry, 2023, 42(12): 100173-100173. doi: 10.1016/j.cjsc.2023.100173
8. [8]
  Xiuzheng Deng , Yi Ke , Jiawen Ding , Yingtang Zhou , Hui Huang , Qian Liang , Zhenhui Kang . Construction of ZnO@CDs@Co₃O₄ sandwich heterostructure with multi-interfacial electron-transfer toward enhanced photocatalytic CO₂ reduction. Chinese Chemical Letters, 2024, 35(4): 109064-. doi: 10.1016/j.cclet.2023.109064
9. [9]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
10. [10]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193
11. [11]
  Hong Dong , Feng-Ming Zhang . Covalent organic frameworks for artificial photosynthetic diluted CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100307-100307. doi: 10.1016/j.cjsc.2024.100307
12. [12]
  Xiuzheng Deng , Changhai Liu , Xiaotong Yan , Jingshan Fan , Qian Liang , Zhongyu Li . Carbon dots anchored NiAl-LDH@In₂O₃ hierarchical nanotubes for promoting selective CO₂ photoreduction into CH₄. Chinese Chemical Letters, 2024, 35(6): 108942-. doi: 10.1016/j.cclet.2023.108942
13. [13]
  Yufei Jia , Fei Li , Ke Fan . Surface reconstruction of Cu-based bimetallic catalysts for electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100255-100255. doi: 10.1016/j.cjsc.2024.100255
14. [14]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
15. [15]
  Tianbo Jia , Lili Wang , Zhouhao Zhu , Baikang Zhu , Yingtang Zhou , Guoxing Zhu , Mingshan Zhu , Hengcong Tao . Modulating the degree of O vacancy defects to achieve selective control of electrochemical CO₂ reduction products. Chinese Chemical Letters, 2024, 35(5): 108692-. doi: 10.1016/j.cclet.2023.108692
16. [16]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
17. [17]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
18. [18]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245
19. [19]
  Qin Cheng , Ming Huang , Qingqing Ye , Bangwei Deng , Fan Dong . Indium-based electrocatalysts for CO₂ reduction to C1 products. Chinese Chemical Letters, 2024, 35(6): 109112-. doi: 10.1016/j.cclet.2023.109112
20. [20]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037

Get Citation

PDF

XML

Metrics

PDF Downloads(26)
Abstract views(668)
HTML views(30)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Methanol Synthesis by COx Hydrogenation over Cu/ZnO/Al2O3 Catalyst via Hydrotalcite-Like Precursors: the Role of CO in the Reactant Mixture

Metrics

通讯作者: 陈斌, bchen63@163.com

Methanol Synthesis by CO_x Hydrogenation over Cu/ZnO/Al₂O₃ Catalyst via Hydrotalcite-Like Precursors: the Role of CO in the Reactant Mixture