文献类型：期刊文献

英文题名：Engineering the Local Microenvironment over Bi Nanosheets for Highly Selective Electrocatalytic Conversion of CO2 to HCOOH in Strong Acid

作者：Qiao, Yan[1];Lai, Wenchuan[1];Huang, Kai[2];Yu, Tingting[2];Wang, Qiyou[3];Gao, Lei[1];Yang, Zhilong[1];Ma, Zesong[1];Sun, Tulai[4,5];Liu, Min[3];Lian, Cheng[2];Huang, Hongwen[1]

机构：[1]Hunan Univ, Coll Mat Sci & Engn, Changsha 410082, Hunan, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem, Shanghai 200237, Peoples R China;[3]Cent South Univ, Sch Phys & Elect, Changsha 410082, Hunan, Peoples R China;[4]Zhejiang Univ Technol, Ctr Electron Microscopy, State Key Lab Breeding Base Green Chem Synth Tech, Hangzhou 310014, Zhejiang, Peoples R China;[5]Zhejiang Univ Technol, Coll Chem Engn, Hangzhou 310014, Zhejiang, Peoples R China

年份：2022

卷号：12

期号：4

起止页码：2357

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20220711634272);WOS:【SCI-EXPANDED(收录号:WOS:000766237100024)】；

基金：This work was supported by the National Key Research and Development Program of China (no. 2021YFA1502000), the NSFC (nos. U2032149 and 22102052), the Science and Technology Innovation Program of Hunan Province (nos. 2021RC3065 and 2021RC2053), the Hunan Provincial Natural Science Foundation of China (no. 2020JJ2001), the Shenzhen Science and Technology Program (no. JCYJ20210324120800002), and the Hefei National Laboratory for Physical Sciences at the Microscale (no. KF2020108).

语种：英文

外文关键词：electrocatalytic CO2 reduction reaction; HCOOH; acidic media; local microenvironment; intermediate stabilization

摘要：The extensive deployment of the electrocatalytic CO2 reduction reaction (CO2RR) is presently limited by the utilization of alkaline/neutral electrolytes in which carbonate formation severely reduces the carbon efficiency and electrolysis stability. By contrast, the CO2RR in a strong acid electrolyte can overcome these shortcomings, yet the hydrogen evolution reaction (HER) greatly outcompetes the CO2RR in acidic media. Herein, CO2 reduction to HCOOH, a significant chemical intermediate in many industrial processes, was realized in strong acid (pH <= 1) through introducing K+ cations into the electrolyte. The K+-assisted acidic CO2RR accordingly manufactured HCOOH with a high Faradaic efficiency of 92.2% @-1.23 V-RHE and a commercially relevant current density of -237.1 mA cm(-2). More importantly, a high single-pass carbon efficiency of 27.4% for HCOOH production was demonstrated in acid, which exceeded the value obtained in the alkaline CO2RR. Further mechanistic studies demonstrated that K+ can engineer the local microenvironment over the Bi catalyst surface by reducing the proton coverage to suppress the competing HER and creating local interaction to stabilize the *OCOH intermediate, which ultimately promotes high-efficiency CO2 conversion to HCOOH in strong acidic media.