Thermodynamic and Kinetic Competition between C-H and O-H Bond Formation Pathways during Electrochemical Reduction of CO on Copper Electrodes

doi:10.1021/acscatal.0c05472

	Thermodynamic and Kinetic Competition between C-H and O-H Bond Formation Pathways during Electrochemical Reduction of CO on Copper Electrodes
	Xiang, Shi-Qin 1; Shi, Jun-Lin 1; Gao, Shu-Ting 1; Zhang, Wei 2; Zhao, Liu-Bin 1
刊名	ACS CATALYSIS
	2021-02-19
卷号	11 期号:4 页码:2422-2434
关键词	CO2 reduction reaction reaction kinetics density functional theory electrocatalytic activity electrocatalytic selectivity copper electrode facet dependence
ISSN号	2155-5435
DOI	10.1021/acscatal.0c05472
通讯作者	Zhang, Wei(andyzhangwei@163.com) ; Zhao, Liu-Bin(lbzhao@swu.edu.cn)
英文摘要	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.
资助项目	Fundamental Research Funds for the Central Universities[XDJK2019C032] ; Open Funds of State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University)[201929] ; Chongqing Talents Program[CQYC201905041] ; Chongqing Graduate Scientific Research Innovation Project[CYS18115]
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000621598700041
内容类型	期刊论文
源URL	[http://119.78.100.138/handle/2HOD01W0/13014]
专题	中国科学院重庆绿色智能技术研究院
通讯作者	Zhang, Wei; Zhao, Liu-Bin
作者单位	1.Southwest Univ, Dept Chem, Sch Chem & Chem Engn, Chongqing 400715, Peoples R China 2.Chinese Acad Sci, Chongqing Inst Green & Intelligent Technol, Chongqing 400714, Peoples R China
推荐引用方式 GB/T 7714	Xiang, Shi-Qin,Shi, Jun-Lin,Gao, Shu-Ting,et al. Thermodynamic and Kinetic Competition between C-H and O-H Bond Formation Pathways during Electrochemical Reduction of CO on Copper Electrodes[J]. ACS CATALYSIS,2021,11(4):2422-2434.
APA	Xiang, Shi-Qin,Shi, Jun-Lin,Gao, Shu-Ting,Zhang, Wei,&Zhao, Liu-Bin.(2021).Thermodynamic and Kinetic Competition between C-H and O-H Bond Formation Pathways during Electrochemical Reduction of CO on Copper Electrodes.ACS CATALYSIS,11(4),2422-2434.
MLA	Xiang, Shi-Qin,et al."Thermodynamic and Kinetic Competition between C-H and O-H Bond Formation Pathways during Electrochemical Reduction of CO on Copper Electrodes".ACS CATALYSIS 11.4(2021):2422-2434.