文献类型：期刊文献

英文题名：Insight into CO Activation over Cu(100) under Electrochemical Conditions

作者：Sheng, Tian[1];Wang, Dong[2,3,4];Lin, Wen-Feng[5];Hu, P.[2,3,4];Sun, Shi-Gang[1]

机构：[1]Xiamen Univ, Collaborat Innovat Ctr Chem Energy Mat, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China;[2]E China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]E China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[4]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland;[5]Univ Loughborough, Dept Chem Engn, Loughborough LE11 3TU, Leics, England

年份：2016

卷号：190

起止页码：446

外文期刊名：ELECTROCHIMICA ACTA

收录：;EI(收录号：20160301820535);WOS:【SCI-EXPANDED(收录号:WOS:000371141500054)】；

基金：Financial supports from the NSFC (21361140374, 21321062, 21333003 and 21573183) are acknowledged.

语种：英文

外文关键词：CO2; copper electrode; electroreduction; density functional theory; ab initio molecular dynamics

摘要：The reduction of CO2 on copper electrodes has attracted great attentions in the last decades, since it provides a sustainable approach for energy restore. During the CO2 reduction process, the electron transfer to COads is experimentally suggested to be the crucial step. In this work, we examine two possible pathways in CO activation, i.e. to generate COHads and CHOads, respectively, by performing the state-of-the-art constrained ab initio molecular dynamics simulations on the charged Cu(100) electrode under aqueous conditions, which is close to the realistic electrochemical condition. The free energy profile in the formation of COHads via the coupled proton and electron transfer is plotted. Furthermore, by Bader charge analyses, a linear relationship between C-O bond distance and the negative charge in CO fragment is unveiled. The formation of COHads is identified to be a surface catalytic reaction, which requires the adsorption of H atom on the surface first. By comparing these two pathways, we demonstrate that kinetically the formation of COHads is more favored than that of COHads, while COHads is thermodynamically more stable. This work reveals that CO activation via COHads intermediate is an important pathway in electrocatalysis, which could provide some insights into CO2 electroreduction over Cu electrodes. Crown Copyright (C) 2016 Published by Elsevier Ltd. All rights reserved.