Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction  

作　　者：Jing Zhang Jia-Jun Dai De-Quan Cao Heng Xu Xing-Yu Ding Chun-Hua Zhen Beate Paulus Jin-Yu Ye Qian Liang Jun-Ke Liu Shi-Jun Xie Sai-Sai Deng Zhen Wang Jun-Tao Li Yao Zhou Shi-Gang Sun 

机构地区：[1]College of Energy,XiamenUniversity,Xiamen 361005,Fujian,China [2]College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian,China [3]Institute of Chemistry and Biochemistry,Freie Universitat Berlin,Arnimallee 22,14195 Berlin,Germany

出　　处：《Journal of Energy Chemistry》2023年第8期313-323,I0009,共12页能源化学（英文版）

基　　金：The National Key Research and Development Program of China(2021YFA1502000 and 2022YFA1505300);the National Natural Science Foundation of China (22288102, 22072124);support from Beijing Synchrotron Radiation Facility (1W1B, BSRF);China Scholarship Council for the financial support。

摘　　要：With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

关 键 词：Metal-organic solid compounds Conjugated coordinative polymer Solid-solid interfacial electron transfer MN_(4)sites Electrocatalysis 

分 类 号：X701[环境科学与工程—环境工程] O631.1[理学—高分子化学] O643.36[理学—化学]