Citation: Xuanye Chen, Wenhua Zhang, Weixin Huang. CO hydrogenation on stepped Cu and CuZn alloy surfaces: Competition between methanol synthesis and methanation pathways[J]. Chinese Chemical Letters, ;2023, 34(7): 107809. doi: 10.1016/j.cclet.2022.107809 shu

CO hydrogenation on stepped Cu and CuZn alloy surfaces: Competition between methanol synthesis and methanation pathways

Xuanye Chen ^{a, b} ,
Wenhua Zhang ^{a, *,} ,
Weixin Huang ^{a, *,}

a.
School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
b.
Research Institute of Applied Chemistry, Jiangxi Academy of Sciences, Nanchang 330096, China

whhzhang@ustc.edu.cn

huangwx@ustc.edu.cn

Received Date: 19 August 2022
Revised Date: 5 September 2022
Accepted Date: 6 September 2022
Available Online: 12 September 2022

Figures(3)

Comprehensive fundamental understanding of CO hydrogenation reactions over Cu and ZnCu alloy surfaces is of great importance. Herein, we report a comparative DFT calculation study of elementary surface reaction network of CO hydrogenation reactions on stepped Cu(211), Cu(611), ZnCu(211) and ZnCu(611) surfaces. On ZnCu(211) and ZnCu(611) surfaces, the energetic favorable reaction path of CO hydrogenation reaction follows CO* → HCO* → H₂CO* → H₃CO* → CH₃OH* → CH₃OH with H₃CO* hydrogenation as the rate-limiting step and proceeds more facilely on ZnCu(611) surface than on ZnCu(211) surface. On Cu(211) and Cu(611) surfaces, the energetic favorable reaction path of CO hydrogenation reaction follows CO* → HCO* → HCOH* → H₂COH* → H₃COH* → CH₃* → CH₄* → CH₄ with H₂COH* hydrogenation as the rate-limiting step and proceeds more facilely on Cu(611) than on Cu(211). The key difference of CO hydrogenation reaction on ZnCu alloy surface and Cu is that the resulting CH₃OH* species desorbs to produce CH₃OH on ZnCu alloy but undergoes H*-assisted decomposition to CH₃* and eventually to CH₄ on Cu surface. These results successfully unveil elementary surface reaction networks and structure sensitivity of Cu and ZnCu alloy-catalyzed CO hydrogenation reactions.
- Theoretical calculation,
- Reaction mechanism,
- Structure-activity relation,
- Facet effect,
- Defect
1. [1]
  W. Chen, R. Pestman, B. Zijlstra, I.A.W. Filot, E.J.M. Hensen, ACS Catal. 7 (2017) 8050-8060. doi: 10.1021/acscatal.7b02757
2. [2]
  W. Chen, I.A.W. Filot, R. Pestman, E.J.M. Hensen, ACS Catal. 7 (2017) 8061-8071. doi: 10.1021/acscatal.7b02758
3. [3]
  K.C. Waugh, Catal. Today15 (1992) 51-75. doi: 10.1016/0920-5861(92)80122-4
4. [4]
  K. Klier, Adv. Catal. 31 (1982) 243-313. doi: 10.1080/02786820290038546
5. [5]
  S. Kuld et al., Science352 (2016) 969-974. doi: 10.1126/science.aaf0718
6. [6]
  F. Studt et al., ChemCatChem 7 (2015) 1105-1111. doi: 10.1002/cctc.201500123
7. [7]
  Y. Choi, K. Futagami, T. Fujitani, J. Nakamura, Catal. Lett. 73 (2001) 27-31. doi: 10.1023/a:1009074219286
8. [8]
  D. Laudenschleger, H. Ruland, M. Muhler, Nat. Commun. 11 (2020) 3898. doi: 10.1038/s41467-020-17631-5
9. [9]
  N.D. Nielsen, J. Thrane, A.D. Jensen, J.M. Christensen, Catal. Lett. 150 (2020) 1427-1433. doi: 10.1007/s10562-019-03036-7
10. [10]
  M. Behrens, et al., Science336 (2012) 893-897. doi: 10.1126/science.1219831
11. [11]
  Z. Zhang, X. Chen, J. Kang et al., Nat. Commun. 12 (2021) 4331. doi: 10.1038/s41467-021-24621-8
12. [12]
  Y.F. Shi, P.L. Kang, C. Shang, Z.P. Liu, J. Am. Chem. Soc. 144 (2022) 13401-13414. doi: 10.1021/jacs.2c06044
13. [13]
  G. Kresse, D. Joubert, Phys. Rev. B 59 (1999) 1758-1775.
14. [14]
  G. Kresse, J. Furthmuller, Phys. Rev. B 54 (1996) 11169-11186. doi: 10.1103/PhysRevB.54.11169
15. [15]
  P.E. Blochl, Phys. Rev. B 50 (1994) 17953-17979. doi: 10.1103/PhysRevB.50.17953
16. [16]
  J.P. Perdew, Y. Wang, Phys. Rev. B 45 (1992) 13244-13249. doi: 10.1103/PhysRevB.45.13244
17. [17]
  J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865-3868. doi: 10.1103/PhysRevLett.77.3865
18. [18]
  F. Studt, F. Abild-Pedersen, J.B. Varley, J.K. Nørskov, Catal. Lett. 143 (2013) 71-73. doi: 10.1007/s10562-012-0947-5
19. [19]
  K.J. Sun, Y.H. Zhao, H.Y. Su, W.X. Li, Theor. Chem. Acc. 131 (2012) 1118-1127. doi: 10.1007/s00214-012-1118-x
20. [20]
  G. Henkelman, H. Jonsson, J. Chem. Phys. 113 (2000) 9978-9985. doi: 10.1063/1.1323224
21. [21]
  G. Henkelman, B.P. Uberuaga, H. Jonsson, J. Chem. Phys. 113 (2000) 9901-9904. doi: 10.1063/1.1329672
22. [22]
  A. Janotti, C.G. Van de Walle, Phys. Rev. B 76 (2007) 165202-165223. doi: 10.1103/PhysRevB.76.165202
23. [23]
  F. Liao, X.P. Wu, J. Zheng, et al., Catal. Sci. Technol. 6 (2016) 7698-7702. doi: 10.1039/C6CY01832G
24. [24]
  F. Liao, X.P. Wu, J. Zheng, et al., Green Chem. 19 (2017) 270-280. doi: 10.1039/C6GC02366E
25. [25]
  X.H. Zhao, Y.W. Li, J.G. Wang, C.F. Huo, J. Fuel Chem. Technol. 39 (2011) 956-960. doi: 10.1016/S1872-5813(12)60004-8
26. [26]
  G. Jia, L. Ling, R. Zhang, B. Wang, Mol. Catal. 518 (2022) 112071. doi: 10.1016/j.mcat.2021.112071
1. [1]
  Bingke Zhang , Dongbo Wang , Jiamu Cao , Wen He , Gang Liu , Donghao Liu , Chenchen Zhao , Jingwen Pan , Sihang Liu , Weifeng Zhang , Xuan Fang , Liancheng Zhao , Jinzhong Wang . Tuning Stark effect by defect engineering on black titanium dioxide mesoporous spheres for enhanced hydrogen evolution. Chinese Chemical Letters, 2024, 35(11): 110254-. doi: 10.1016/j.cclet.2024.110254
2. [2]
  Peiyang Du , Ling Yuan , Tong Bao , Yamin Xi , Jiaxin Li , Yin Bi , Luli Yin , Jing Wang , Chao Liu . Facet effect of metal-organic frameworks on supporting co-catalysts for photocatalytic hydrogen peroxide production. Chinese Chemical Letters, 2025, 36(11): 110472-. doi: 10.1016/j.cclet.2024.110472
3. [3]
  Zhi Zhu , Xiaohan Xing , Qi Qi , Wenjing Shen , Hongyue Wu , Dongyi Li , Binrong Li , Jialin Liang , Xu Tang , Jun Zhao , Hongping Li , Pengwei Huo . Fabrication of graphene modified CeO2/g-C3N4 heterostructures for photocatalytic degradation of organic pollutants. Chinese Journal of Structural Chemistry, 2023, 42(12): 100194-100194. doi: 10.1016/j.cjsc.2023.100194
4. [4]
  Xiaodong Zhang , Bohui Xu , Deshuai Xiao , Xinyuan Zhang , Pifu Gong , Zheshuai Lin . From centrosymmetric CN3H6C6H5SO3 to non-centrosymmetric CN3H6C6H4SO3(OH): Hydroxyl introduced hydrogen bond reconstruction to realize strong second harmonic generation. Chinese Journal of Structural Chemistry, 2025, 44(10): 100707-100707. doi: 10.1016/j.cjsc.2025.100707
5. [5]
  Shaohua Zhang , Xiaojuan Dai , Wei Hao , Liyao Liu , Yingqiao Ma , Ye Zou , Jia Zhu , Chong-an Di . A first-principles study of the Nernst effect in doped polymer. Chinese Chemical Letters, 2024, 35(12): 109837-. doi: 10.1016/j.cclet.2024.109837
6. [6]
  Yanhui Lu , Chengang Pei , Wenqiang Li , Qing Liu , Huan Pang , Xu Yu . Tailoring active sites of cerium and nitrogen Co-doped rhenium disulfide for enhanced hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(12): 111646-. doi: 10.1016/j.cclet.2025.111646
7. [7]
  Yingfen Li , Zhiqi Wang , Yunhai Zhao , Dajun Luo , Xueliang Zhang , Jun Zhao , Zhenghua Su , Shuo Chen , Guangxing Liang . Potassium doping for grain boundary passivation and defect suppression enables highly-efficient kesterite solar cells. Chinese Chemical Letters, 2024, 35(11): 109468-. doi: 10.1016/j.cclet.2023.109468
8. [8]
  Hongtao Wang , Yingzhang Shi , Jiayi Guo , Shuzhao Sun , Wenda Zhang , Zhiwen Wang , Yujie Song , Dongpeng Yan . CdS clusters induced defect on NH₂−MIL-125(Ti) nanosheets for improving photocatalytic synthesis of N-benzylidene benzylamine. Chinese Chemical Letters, 2025, 36(10): 110779-. doi: 10.1016/j.cclet.2024.110779
9. [9]
  Chunrui Zhao , Tianren Li , Jiage Li , Yansong Liu , Zian Fang , Xinyu Wang , Mingxin Huo , Shuangshi Dong , Mingyu Li . Doped cobalt for simultaneously promoting active (001) facet exposure of MIL-68(In) and acting as reactive sites in peroxymonosulfate-mediated photocatalytic decontamination. Chinese Chemical Letters, 2025, 36(5): 110201-. doi: 10.1016/j.cclet.2024.110201
10. [10]
  Jianfang Cao , Xue Ma , Xinyu Chen , Tianci Zhang , Wen Sun . Theoretical perspective on fine-tuning ISC efficiency in D-A BODIPY photosensitizers through heteroatom incorporation and nitrogen ring strain modulation. Chinese Chemical Letters, 2025, 36(10): 110897-. doi: 10.1016/j.cclet.2025.110897
11. [11]
  Pin Cui , Ying Tang , Jie Yu , Zhen Yang , Shouhua Yang , Boqin Li , Gang Wang , Huan Pang , Feng Yu . Bimetallic ZnFe–NC prepared using microchannel reactor for oxygen reduction reaction and mechanism research. Chinese Chemical Letters, 2025, 36(9): 110303-. doi: 10.1016/j.cclet.2024.110303
12. [12]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
13. [13]
  Da Yue , Tanglue Feng , Zhicheng Zhu , Mingcheng Zhang , Liyuan Chen , Xiao Han , Haizhu Sun , Bai Yang . Carbonized polymer dots confined active Ru-O sites for boosting electrocatalytic oxygen evolution. Chinese Chemical Letters, 2025, 36(11): 111393-. doi: 10.1016/j.cclet.2025.111393
14. [14]
  Chongbei Wu , Benzhi Wang , Xuan Li , Jiaxuan Gu , Yihan Wu , Zhe Zhao , Pengfei Jia , Jizhou Jiang . Dual activation pathways based on OH-functionalized alk-Ti₃C₂ MXene/RuO_x boosting the hydrogen generation. Chinese Chemical Letters, 2025, 36(8): 111162-. doi: 10.1016/j.cclet.2025.111162
15. [15]
  Miaosen Yang , Junyang Ding , Zhiwei Wang , Jingwen Zhang , Zimo Peng , Xijun Liu . NiMo-based alloy and its sulfides for energy-saving hydrogen production via sulfion oxidation assisted alkaline seawater splitting. Chinese Chemical Letters, 2025, 36(9): 110861-. doi: 10.1016/j.cclet.2025.110861
16. [16]
  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
17. [17]
  Tingting Liu , Pengfei Sun , Wei Zhao , Yingshuang Li , Lujun Cheng , Jiahai Fan , Xiaohui Bi , Xiaoping Dong . Magnesium doping to improve the light to heat conversion of OMS-2 for formaldehyde oxidation under visible light irradiation. Chinese Chemical Letters, 2024, 35(4): 108813-. doi: 10.1016/j.cclet.2023.108813
18. [18]
  Xin Zhou , Xuejia Li , Yujia Xiang , Heng Zhang , Chuanshu He , Zhaokun Xiong , Wei Li , Peng Zhou , Hongyu Zhou , Yang Liu , Bo Lai . The application of low-valent sulfur oxy-acid salts in advanced oxidation and reduction processes: A review. Chinese Chemical Letters, 2025, 36(9): 110664-. doi: 10.1016/j.cclet.2024.110664
19. [19]
  Jiaming Li , Na Xu , Yafei Zhang , Hongjun Dong , Chunmei Li . Research progress of heterogeneous photocatalyst for H₂O₂ production: A mini review. Chinese Chemical Letters, 2025, 36(11): 110470-. doi: 10.1016/j.cclet.2024.110470
20. [20]
  Linyu Zhu , Xu Tian , Guang Shi , Wenchi Zhang , Peisong Tang , Mohamed Bououdina , Sajjad Ali , Pengfei Xia . Assembling 3D cross-linked network by carbon nitride nanowires for visible-light photocatalytic H₂ evolution from dyestuffs wastewater. Chinese Chemical Letters, 2025, 36(12): 111088-. doi: 10.1016/j.cclet.2025.111088

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(1332)
HTML views(103)

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