文献类型：期刊文献

英文题名：Operando Converting BiOCl into Bi2O2(CO3)xCly for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate

作者：Fu, Huai Qin[1];Liu, Junxian[1];Bedford, Nicholas M.[2];Wang, Yun[1];Wright, Joshua[3];Liu, Peng Fei[4];Wen, Chun Fang[4];Wang, Liang[1];Yin, Huajie[1];Qi, Dongchen[5];Liu, Porun[1];Yang, Hua Gui[4];Zhao, Huijun[1]

机构：[1]Griffith Univ, Ctr Catalysis & Clean Energy, Gold Coast Campus, Gold Coast, Qld 4222, Australia;[2]Univ New South Wales, Sch Chem Engn, Sydney, NSW 2052, Australia;[3]IIT, Dept Phys, Chicago, IL 60616 USA;[4]East China Univ Sci & Technol, Sch Mat Sci & Engn, Minist Educ, Key Lab Ultrafine Mat, Shanghai 200237, Peoples R China;[5]Queensland Univ Technol, Sch Chem & Phys, Ctr Mat Sci, Brisbane, Qld 4001, Australia

年份：2022

卷号：14

期号：1

外文期刊名：NANO-MICRO LETTERS

收录：;EI(收录号：20221912091066);WOS:【SCI-EXPANDED(收录号:WOS:000790259600002)】；

基金：This work was financially supported by Australian Research Council Discovery Project (DP200100965). Bi L3-edge XAS measurements were performed at the 10-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Operations at 10-ID-B are further supported by members of the Materials Research Collaborative Access Team. C and O K-edge measurements were performed at the SXR beamline of the Australian Synchrotron, part of the Australian Nuclear Science and Technology Organisation.

语种：英文

外文关键词：Carbon dioxide reduction; Chloride-containing bismuth subcarbonate; Cathodic potential-promoted anion-exchange; Stability

摘要：Bismuth-based materials (e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO2 to formate. However, Bi-o-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 CO2RR conditions. A synthetic approach is developed to electrochemically convert BiOCl into Cl-containing subcarbonate (Bi2O2(CO3)(x)Cl-y) under operando CO2RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi2O2(CO3)(x)Cl-y via a cathodic potential-promoted anion-exchange process. The operando synthesized Bi2O2(CO3)(x)Cl-y can tolerate - 1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi2O2CO3, the formation of metallic Bi-o occurs at - 0.6 V versus RHE. At - 0.8 V versus RHE, Bi2O2(CO3)(x)Cl-y can readily attain a FEHCOO- of 97.9%, much higher than that of the pure Bi2O2CO3 (81.3%). DFT calculations indicate that differing from the pure Bi2O2CO3-catalyzed CO2RR, where formate is formed via a (OCHO)-O-* intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of HCOO- over Bi2O2(CO3)(x)Cl-y has proceeded via a (COOH)-C-* intermediate step that only requires low energy input of 2.56 eV.