Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO_(2) to Formic Acid  

作　　者：ZHAO Sirui ZHOU Heng CAO Dengfeng SHENG Beibei QIAN Fangren LIU Chongjing CHU Yongheng LI Rongyao SONG Li CHEN Shuangming 

机构地区：[1]National Synchrotron Radiation Laboratory,Key Laboratory of Precision and Intelligent Chemistry,University of Science and Technology of China,Hefei 230029,P.R.China [2]SINOPEC Shanghai Research Institute of Petrochemical Technology Co.,Ltd.,Shanghai 201208,P.R.China

出　　处：《Chemical Research in Chinese Universities》2025年第2期273-280,共8页高等学校化学研究(英文版)

基　　金：supported by the National Key Research and Development Program of China(No.2024YFA1509501);the National Natural Science Foundation of China(Nos.12322515,U23A20121,12225508,12305370);the Youth Innovation Promotion Association of CAS(No.2022457);the China Postdoctoral Science Foundation(Nos.BX20220282,2022M720136);the Anhui Provincial Natural Science Foundation,China(No.2308085QA16).

摘　　要：Electrocatalytic reduction reaction of carbon dioxide(CO_(2)RR)to formic acid is widely considered an effective strategy for addressing the greenhouse effect and enhancing energy conversion efficiency.However,existing catalytic systems are severely hampered by insufficient activity and significant hydrogen evolution reaction(HER),which substantially compromises the selectivity and stability of CO_(2)RR,necessitating the development of highly efficient and stable electrocatalysts.Herein,we present a heteroatomic modification strategy to synthesize B-doped Bi and N-doped Bi electrocatalysts,and systematically investigate the regulation mechanism of incorporated elements on the electronic environment using X-ray absorption fine structure(XAFS)spectroscopy and other characterization techniques.The optimized B-doped Bi catalyst demonstrates exceptional catalytic performance,achieving a remarkable Faradaic efficiency of 95%for formic acid production at a high current density of−190 mA/cm2 under alkaline conditions,while maintaining excellent stability for 20 h.Through comprehensive experimental characterization and theoretical calculations,we reveal that the B-doping-induced electron-rich structure significantly promotes CO_(2) molecule activation and facilitates the formation of the key intermediate*OCHO,thereby achieving high selectivity and stability in CO_(2)RR.This work not only elucidates the crucial role of electronic environment in CO_(2) electrocatalytic conversion but also provides innovative insights into the rational design of high-performance electrocatalysts.

关 键 词：Electrocatalytic carbon dioxide reduction reaction Synchrotron radiation spectroscopy Heteroatom doping Electronic environment modulation 

分 类 号：O643.36[理学—物理化学]