Electronic perturbation of Cu nanowire surfaces with functionalized graphdiyne for enhanced CO_(2)reduction reaction  

作　　者：Haiyuan Zou Dongfang Cheng Chao Tang Wen Luo Huatian Xiong Hongliang Dong Fan Li Tao Song Siyan Shu Hao Dai Ziang Cui Zhouguang Lu Lele Duan 

机构地区：[1]Department of Chemistry,Southern University of Science and Technology,Shenzhen 518055,China [2]Department of Chemical and Biomolecular Engineering,University of California Los Angeles,Los Angeles 90095,USA [3]Department of Materials Science and Engineering,Southern University of Science and Technology,Shenzhen 518055,China [4]Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry,School of Science,Westlake University,Hangzhou 310030,China [5]Center for High-Pressure Science and Technology Advanced Research,Shanghai 201203,China [6]Department of Chemistry,Tsinghua University,Beijing 100084,China [7]Division of Solar Energy Conversion and Catalysis at Westlake University,Zhejiang Baima Lake Laboratory Co.,Ltd,Hangzhou 310000,China [8]Institute of Natural Sciences,Westlake Institute for Advanced Study,Hangzhou 310024,China

出　　处：《National Science Review》2024年第12期22-31,共10页国家科学评论(英文版)

基　　金：supported by the National Natural Science Foundation of China(22179057,L.D.;92372114,Z.L.);the start-up package from Westlake University(L.D.).

摘　　要：Electronic perturbation of the surfaces of Cu catalysts is crucial for optimizing electrochemical CO_(2)reduction activity,yet still poses great challenges.Herein,nanostructured Cu nanow ires(NW)w ith fine-tuned surface electronic structure are achieved via surface encapsulation with electron-w ithdraw ing(-F)and-donating(-Me)group-functionalized graphdiynes(R-GDY,R=-F and-Me)and the resulting catalysts,denoted as R-GDY/Cu NW,display distinct CO_(2)reduction performances.In situ electrochemical spectroscopy revealed that the^(*)CO(a key intermediate of the CO_(2)reduction reaction)binding affinity and consequent^(*)CO coverage positively correlate with the Cu surface oxidation state,leading to favorable C-C coupling on F-GDY/Cu NW over Me-GDY/Cu NW.Electrochemical measurements corroborate the favorable C_(2)H_(4)production with an optimum C_(2+)selectivity of 73.15%±2.5%observed for F-GDY/Cu NW,while the predominant CH_(4)production is favored by Me-GDY/Cu NW.Furthermore,by leveraging the^(*)Cu-hydroxyl(OH)/^(*)CO ratio as a descriptor,mechanistic investigation reveals that the protonation of distinct adsorbed^(*)CO facilitated by^(*)Cu-OH is crucial for the selective generation of C_(2)H_(4)and CH_(4)on F-GDY/Cu NW and Me-GDY/Cu NW,respectively.

关 键 词：CO_(2)reduction reaction copper nanowire group-functionalized graphdiyne surface electronic perturbation 

分 类 号：TQ426[化学工程] TB383.1[一般工业技术—材料科学与工程] X701[环境科学与工程—环境工程]