Operando Converting BiOCl into Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate  

作　　者：Huai Qin Fu Junxian Liu Nicholas M.Bedford Yun Wang Joshua Wright Peng Fei Liu Chun Fang Wen Liang Wang Huajie Yin Dongchen Qi Porun Liu Hua Gui Yang Huijun Zhao 

机构地区：[1]Centre for Catalysis and Clean Energy,Gold Coast Campus,Griffith University,Gold Coast,QLD 4222,Australia [2]School of Chemical Engineering,University of New South Wales,Sydney,NSW 2052,Australia [3]Department of Physics,Illinois Institute of Technology,Chicago,IL 60616,USA [4]Key Laboratory for Ultrafine Materials of Ministry of Education,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,People’s Republic of China [5]Centre for Materials Science,School of Chemistry and Physics,Queensland University of Technology,Brisbane,QLD 4001,Australia

出　　处：《Nano-Micro Letters》2022年第7期263-278,共16页纳微快报（英文版）

基　　金：financially supported by Australian Research Council Discovery Project(DP200100965)。

摘　　要：Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO_(2)RR conditions. A synthetic approach is developed to electrochemically convert Bi^(O)Cl into Cl-containing subcarbonate(Bi_(2)O_(2)(CO_(3))_(x)Cl_(y)) under operando CO_(2)RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) via a cathodic potential-promoted anion-exchange process. The operando synthesizedBi_(2)O_(2)(CO_(3))_(x)Cl_(y) can tolerate-1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi_(2)O_(2)CO_(3),the formation of metallic Bio occurs at-0.6 V versus RHE. At-0.8 V versus RHE, Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) can readily attain a FEHCOO-of 97.9%,much higher than that of the pure Bi_(2)O_(2)CO_(3)(81.3%). DFT calculations indicate that differing from the pure Bi_(2)O_(2)CO_(3)-catalyzed CO_(2)RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of H COO-over Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV.

关 键 词：Carbon dioxide reduction Chloride-containing bismuth subcarbonate Cathodic potential-promoted anion-exchange Stability 

分 类 号：TQ426[化学工程] X701[环境科学与工程—环境工程]