Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO2 reduction reaction on copper electrodes

doi:10.1039/c9cp06824d

	Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO2 reduction reaction on copper electrodes
	Gao, Shu-Ting 2; Xiang, Shi-Qin 2; Shi, Jun-Lin 2; Zhang, Wei 1; Zhao, Liu-Bin 2
刊名	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
	2020-05-07
卷号	22 期号:17 页码:9607-9615
ISSN号	1463-9076
DOI	10.1039/c9cp06824d
通讯作者	Zhang, Wei(andyzhangwei@163.com) ; Zhao, Liu-Bin(lbzhao@swu.edu.cn)
英文摘要	The electrochemical reduction of CO2 is a promising route for converting intermittent renewable energy into storable fuels and useful chemical products. A theoretical investigation of the reaction mechanism and kinetics is beneficial for understanding the electrocatalytic activity and selectivity. In this report, a kinetic model based on Marcus theory is developed to compute the potential-dependent reaction barrier of the elementary concerted proton-electron transfer steps of electrochemical CO2 reduction reactions, different from the previous hydrogen atom transfer model. It is found that the onset potentials and rate-determining steps for CO and CH4 formation are determined by the first and third concerted proton-electron transfer steps C1 and C3. The influence of binding energy, electrode potential, and reorganization energy on the computed reaction barriers of the C1 and C3 reactions is discussed. In general, the calculated reaction barrier shows a quadratic relationship with the applied electrode potential. Specifically, the reaction barrier is merely determined by the reorganization energy at equilibrium potential. The present kinetic model is applied to compare the electrocatalytic activities in the electrochemical reduction of CO2 on various copper crystal surfaces. Among the four studied copper single-crystal surfaces, Cu(211) exhibits the best electrocatalytic activity for CO formation and CH4 formation due to its low onset potential and overpotential.
资助项目	National Natural Science Foundation of China[21603176] ; Youth Innovation Promotion Association of the Chinese Academy of Sciences[2015316] ; Chongqing Talents Program[CQYC201905041] ; Fundamental Research Funds for the Central Universities[XDJK2019C032] ; State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University)[201706]
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000532479300043
内容类型	期刊论文
源URL	[http://119.78.100.138/handle/2HOD01W0/11022]
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.Chinese Acad Sci, Chongqing Inst Green & Intelligent Technol, Chongqing 400714, Peoples R China 2.Southwest Univ, Sch Chem & Chem Engn, Dept Chem, Chongqing 400715, Peoples R China
推荐引用方式 GB/T 7714	Gao, Shu-Ting,Xiang, Shi-Qin,Shi, Jun-Lin,et al. Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO2 reduction reaction on copper electrodes[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2020,22(17):9607-9615.
APA	Gao, Shu-Ting,Xiang, Shi-Qin,Shi, Jun-Lin,Zhang, Wei,&Zhao, Liu-Bin.(2020).Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO2 reduction reaction on copper electrodes.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,22(17),9607-9615.
MLA	Gao, Shu-Ting,et al."Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO2 reduction reaction on copper electrodes".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 22.17(2020):9607-9615.