The role of copper in enhancing the performance of heteronuclear diatomic catalysts for the electrochemical CO_(2)conversion to C_(1) chemicals  

作　　者：Qi Zhao Rachel Crespo-Otero Devis Di Tommaso 

机构地区：[1]Department of Chemistry,School of Physical and Chemical Sciences,Queen Mary University of London,London E14NS,UK [2]Department of Chemistry,University College London,London WC1H 0AJ,UK

出　　处：《Journal of Energy Chemistry》2023年第10期490-500,I0013,共12页能源化学（英文版）

基　　金：the China Scholarship Council for financial support;the funding by the Leverhulme Trust(RPG2019-122);the ACT program(Accelerating CCS Technologies,Horizon2020 Project No.294766),which funded the FUNMIN project;Financial contributions were made from Department for Business,Energy&Industrial Strategy(BEIS)together with extra funding from NERC and EPSRC research councils,United Kingdom,ADEME(FR),MINECO-AEI(ES);partially funded by EPSRC(EP/P020194/1);funded by EPSRC(EP/L000202);supported by QMUL Research-IT。

摘　　要：Diatomic catalysts(DACs)with two adjacent metal atoms supported on graphene can offer diverse functionalities,overcoming the inherent limitations of single atom catalysts(SACs).In this study,density functional theory calculations were conducted to investigate the reactivity of the carbon dioxide(CO_(2))reduction reaction(CO_(2)RR)on metal sites of both DACs and SACs,as well as their synergistic effects on activity and selectivity.Calculation of the Gibbs free energies of CO_(2)RR and associated values of the limiting potentials to generate C_(1) products showed that Cu acts as a promoter rather than an active catalytic centre in the catalytic CO_(2)conversion on heteronuclear DACs(CuN_(4)-MN_(4)),improving the catalytic activity on the other metal compared to the related SAC MN_(4).Cu enhances the initial reduction of CO_(2)by promoting orbital hybridization between the key intermediate*COOH 2p-orbitals and the metals 3d-orbitals around the Fermi level.This degree of hybridization in the DACs CuN_(4)-MN_(4) decreases from Fe to Co,Ni,and Zn.Our work demonstrates how Cu regulates the CO_(2)RR performance of heteronuclear DACs,offering an effective approach to designing practical,stable,and high-performing diatomic catalysts for CO_(2)electroreduction.

关 键 词：Electrocatalytic CO_(2)reduction Single atom catalysts Diatomic catalysts Graphene Density functional theory calculations 

分 类 号：O643.36[理学—物理化学]