Theoretical Study on Menchanism of Water-Gas Shift Reaction Catalyzed by Binary Copper Cluster

doi:10.6023/A14110790

Acta Chim. Sinica ›› 2015, Vol. 73 ›› Issue (4): 343-348.DOI: 10.6023/A14110790 Previous Articles Next Articles

Article

二元铜团簇催化水煤气变换反应机理的理论研究

任宁宁, 郭玲, 董晓娜, 文彩霞

山西师范大学化学与材料科学学院山西师范大学现代文理学院山西临汾 041004

投稿日期:2014-11-18 发布日期:2015-01-28
通讯作者: 郭玲 E-mail:840080528@qq.com
基金资助:
项目受山西省自然科学基金(No. 2013011009-6), 山西省高等学校131领军人才工程项目和山西省高等学校大学生创新创业训练项目(No. 2015537)资助.

Theoretical Study on Menchanism of Water-Gas Shift Reaction Catalyzed by Binary Copper Cluster

Ren Ningning, Guo Ling, Dong Xiaona, Wen Caixia

School of Chemistry and Material Science, Shanxi Normal University; Shanxi Normal University of Modern Arts and Science, Linfen 041004, Shanxi Province, China

Received:2014-11-18 Published:2015-01-28
Supported by:
Project supported by the Natural Science Foundation of Shanxi Province (Grant No. 2013011009-6), the High School 131 Leading Talent Project of Shanxi and Training Programs for Innovation and Entrepreneurship of Shanxi Province (No. 2015537).

1. Theoretical Study on Menchanism of Water-Gas Shift Reaction Catalyzed by Binary Copper Cluster.PDF(4631KB)

Abstract

The water-gas shift reaction (WGSR) is an important reaction system and can be applied for removing small amounts of CO from H₂-rich gases for polymer electrolyte membrane fuel cells. However, the mechanism of the reaction is still in dispute. In order to clarify the mechanism of WGSR, the detailed mechanisms of WGSR on a series of binary clusters Cu₆TM (TM=Co, Rh, Ir, Ni, Pd, Pt, Ag, Au) were investigated by density functional theory, using the PBE functional along with the Lanl2dz basis for metals and 6-311++G(d,p) for non-metals in this paper. The computational results indicated that the absorption of CO molecules on Cu₆TM is easier than that of H₂O. WGSR mechanism involves the redox, carboxyl and formate pathways, which correspond to CO^*+O^*→CO₂(g), CO^*+OH^*→COOH^*→CO₂(g)+H^*, and CO^*+H^*+O^*→CHO^*+O^*→HCOO^**→CO₂(g)+H^*, respectively. The experimentally most observed formate can be attributed to its lower formation and higher dissociation barriers. And dopant Co, Rh, Ni and Pd on copper cluster can have more beneficial effects than pure copper on the catalytic activity. Furthermore, the role of formate, a spectator or key intermediate, on Cu₆TM (TM=Co, Rh, Ni, Pd) surfaces has been investigated. WGSR activity has been determined from the initial CO consumption and final CO₂ product rates. The calculation results show that WGSR is mostly follows the redox pathway on Cu₆TM (TM=Ni, Pd) surface due to the lower CO oxidation barriers; on the other hand, all the three pathways contribute similarly in WGSR on Cu₆TM (TM=Co, Rh) surfaces. The results can help us to understand the catalytic behavior in experiment, design better catalysts, and, therefore, move one step forward to enable hydrogen economy to the practical application.

Key words: density functional theory, water-gas shift reaction, mechanism, binary copper cluster

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Ren Ningning, Guo Ling, Dong Xiaona, Wen Caixia. Theoretical Study on Menchanism of Water-Gas Shift Reaction Catalyzed by Binary Copper Cluster[J]. Acta Chim. Sinica, 2015, 73(4): 343-348.

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二元铜团簇催化水煤气变换反应机理的理论研究

Theoretical Study on Menchanism of Water-Gas Shift Reaction Catalyzed by Binary Copper Cluster

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