Sm and S Co-doping to Construct Homo-hetero Cu Catalysts for Synergistic Enhancing CO_(2) Electroreduction  

作　　者：Jiyuan Liu Pengsong Li Jiahui Bi Yong Wang Qinggong Zhu Xiaofu Sun Jianling Zhang Zhimin Liu Buxing Han 

机构地区：[1]Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190 China [2]School of Chemical Science, University of Chinese Academy of Sciences, Beijing, 100049 China [3]Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062 China

出　　处：《Chinese Journal of Chemistry》2023年第12期1443-1449,共7页中国化学（英文版）

基　　金：the National Natural Science Foundation of China(22022307,22279146,22102192,22033009,21890761,22121002);CAS Project for Young Scientists in Basic Research(Grant No.YSBR-050);the National Key Research and Development Program of China(2020YFA0710203);Photon Science Center for Carbon Neutrality,and China Postdoctoral Science Foundation(BX20200336 and 2020M680680);In situ X-ray adsorption spectroscopy was conducted at 1W2B beamline station of Beijing Synchrotron Radiation Facility.

摘　　要：Copper(Cu)is recognized as one of the most efficient metal catalysts that can perform the electrocatalytic CO_(2) reduction reaction(CO_(2)RR)and its surface oxidation state determines the reaction pathway.The Cuδ+(0<δ<1)species,are well known active sites in CO_(2)RR to produce hydrocarbons and oxygenates.However,Cuδ+active sites are difficult to control,and it is very easy to be reduced to Cu^(0) under CO_(2)RR operating conditions.Herein,we report a homo-hetero doping strategy to construct an efficient samarium(Sm)and sulfur(S)co-doping catalyst(Smx-CuSy)for CO_(2)RR to formic acid(HCOOH).At optimum conditions,Smx-CuSy delivered a high HCOOH Faradaic efficiency(FE)of 92.1%at the current density of 300 mA·cm^(–2) using 1 mol/L KOH aqueous solution as electrolyte,and the reduction potential was as low as–0.52 V vs.reversible hydrogen electrode(RHE).The co-doping of Sm and S resulted in excellent CO_(2)RR performance owing to the synergistic effect of the homo-hetero structure.The homo-doping of S could effectively adjust the electronic structure of Cu in favor of the formation of abundant Cu^(δ+)species.The existence of hetero-Sm species could not only stabilize the Cu^(δ+)sites,but also increase the concentration of H ions to form a favorable catalytic environment for HCOOH generation.

关 键 词：Carbon dioxide ELECTROCHEMISTRY LANTHANIDES Homo-hetero doping Copper 

分 类 号：O64[理学—物理化学]