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Thermodynamic and Kinetic Competition between C-H and O-H Bond Formation Pathways during Electrochemical Reduction of CO on Copper Electrodes
Xiang, Shi-Qin1; Shi, Jun-Lin1; Gao, Shu-Ting1; Zhang, Wei2; Zhao, Liu-Bin1
2021-02-19
摘要Carbon monoxide is the key intermediate in the electrochemical CO2 reduction reaction and determines the overpotentials and selectivities for C-1 and C-2 products on copper electrodes. The kinetic model based on Marcus charge transfer theory was applied to understand the competing C-H and O-H bond formation pathways involved in the CO reduction reaction on different facets of copper. The electrochemical reduction of CO adopts a thermodynamics-controlled CHO* pathway on Cu(110) and Cu(211) surfaces, and it follows a kinetics-controlled COH* pathway on Cu(111) and Cu(100) surfaces. It was found that the initial competing hydrogenation of CO to produce the CHO* or COH* intermediate plays an important role in determining the catalytic activity and selectivity. The simulated potential-dependent rate constant profiles show that the catalytic activity increases as Cu(111) < Cu(110) < Cu(211) < Cu(100). We suggest that catalyst structure engineering, aiming to decrease the onset potential of the COH* pathway with a lower reaction activation barrier, could be an effective way to promote the electrocatalytic activity of the CO reduction reaction.
关键词CO2 reduction reaction reaction kinetics density functional theory electrocatalytic activity electrocatalytic selectivity copper electrode facet dependence
DOI10.1021/acscatal.0c05472
发表期刊ACS CATALYSIS
ISSN2155-5435
卷号11期号:4页码:2422-2434
通讯作者Zhang, Wei(andyzhangwei@163.com) ; Zhao, Liu-Bin(lbzhao@swu.edu.cn)
收录类别SCI
WOS记录号WOS:000621598700041
语种英语