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
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