Why do CuAl catalysts outperform in CO_(2) electro-reduction to C_(2)H_(4)?  

作　　者：Dongfang Cheng Gong Zhang Lulu Li Xiangcheng Shi Wenjin Zhu Xintong Yuan Lyudmila Moskaleva Peng Zhang Zhi-Jian Zhao Jinlong Gong 

机构地区：[1]Key Laboratory for Green Chemical Technology of Ministry of Education,School of Chemical Engineering and Technology,Tianjin University Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300072,China [2]Joint School of National University of Singapore and Tianjin University,International Campus of Tianjin University,Fuzhou 350207,China [3]Department of Chemistry,University of the Free State,Bloemfontein 9301,South Africa [4]Haihe Laboratory of Sustainable Chemical Transformations,Tianjin 300192,China [5]National Industry-Education Platform of Energy Storage,Tianjin University,Tianjin 300350,China [6]International Joint Laboratory of Low-carbon Chemical Engineering,Tianjin 300192,China [7]Tianjin Normal University,Tianjin 300387,China

出　　处：《Science China Chemistry》2025年第2期763-771,共9页中国科学(化学英文版)

基　　金：supported by the National Key R&D Program of China(2022YFE0102000);the National Natural Science Foundation of China(22121004,U22A20409);the Haihe Laboratory of Sustainable Chemical Transformations,the Program of Introducing Talents of Discipline to Universities(BP0618007);the XPLORER PRIZE for financial support.

摘　　要：Highly efficient CO_(2) electroreduction(CO_(2)RR)holds the promise of closing the carbon cycle.However,the strategies for enhancing activity and selectivity for single C2+ products are still limited.This paper describes the oxophilicity of doped metals on copper(Cu)as a key descriptor for predicting the selectivity in the production of ethylene and ethanol in CO_(2)RR.Our findings reveal a volcano-like relationship between the*O binding energy and catalytic activity,with aluminum(Al)-doped Cu alloys situated at the peak.The strong Al–O bond facilitates C–O bond cleavage,thereby promoting C_(2)H_(4) formation.Through grand canonical density functional theory(GCDFT)calculations,we elucidate the significance of strong oxygen affinity in enhancing*CO_(2) adsorption,leading to its activation into a bidentate-adsorbed form.Moreover,our results demonstrate that Al doping promotes C–C coupling by altering the adsorption mode of the key intermediate *OCCO,shifting it from a less favorable boattype to a more stable chair-type configuration.This modification significantly contributes to the improved catalytic activity for C2+products on CuAl catalysts.Our research provides a detailed mechanistic insight into the high activity and selectivity observed in CO_(2)RR to ethylene on CuAl catalysts,underscoring the critical role of metal oxophilicity in enhancing CO_(2)RR performance.

关 键 词：CO_(2)RR dilute alloy DESCRIPTOR surface oxophilicity 

分 类 号：X701[环境科学与工程—环境工程] O643.36[理学—物理化学] TQ221.211[理学—化学]