Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO_(2) reduction  

作　　者：Yuxiang Zhang Jia Zhao Sen Lin 

机构地区：[1]State Key Laboratory of Photocatalysis on Energy and Environment,College of Chemistry,Fuzhou University,Fuzhou,350002,China [2]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry,Xiamen,361005,China

出　　处：《Chinese Journal of Structural Chemistry》2024年第11期18-26,共9页结构化学(英文)

基　　金：supported by the National Natural Science Foundation of China(22373017);the“Chuying Program”for the Top Young Talents of Fujian Province.

摘　　要：The electrocatalytic CO_(2) reduction reaction(CO_(2)RR)represents an effective way to address energy crises and environmental issues by converting CO_(2) into valuable chemicals.Single-atom catalysts(SACs)can achieve excellent catalytic activity in CO_(2)RR.However,the study of CO_(2)RR on SACs still poses significant challenges,especially in terms of controlling the selectivity towards the deep product such as CH4 and CH3OH.Herein,we employ density functional theory(DFT)calculations to investigate the CO_(2)RR on Cu SAC supported on N-doped graphene(Cu-N/C)and explore the role of N dopants on the CO_(2)RR performance.Compared to Cu SACs sup-ported on N-doped defective graphene with double vacancy(Cu-N/C-DV),Cu SACs supported on N-doped defective graphene with single vacancy(Cu-N/C-SV)can effectively convert CO_(2) into the deeply reduced C1 products,including CH_(4) and CH_(3)OH,thus further indicating that Cu-N/C-SV has a stronger interaction with*CO,which is conducive to the deep reduction of*CO.Increasing the coordination number of N atoms or the proximity of doping site to the Cu active site can effectively enhance the stability of catalyst and promote the adsorption of*CO on Cu-N/C-SV.However,this also increases the free energy of the formation of*CHO intermediate.The results suggest that CuC3-Nm,which contains a N atom in the second coordination shell(meta-position)of Cu SACs,has the best electrocatalytic performance of CO_(2)RR in terms of both selectivity and catalytic activity,not only contributing to an in-depth understanding of the reaction mechanism of CO_(2)RR on SACs but also providing insights into the design of SACs for efficient CO_(2)RR.

关 键 词：Electrocatalytic CO_(2)reduction Cu single-atom catalysts Density functional theory Coordination environment 

分 类 号：O64[理学—物理化学]