Electrochemical CO_(2)-reduction reaction(CO_(2)RR)is a promising way to alleviate energy crisis and excessive carbon emission.The Cu-based electrocatalysts have been considered for CO_(2)RR to generate hydrocarbons a...Electrochemical CO_(2)-reduction reaction(CO_(2)RR)is a promising way to alleviate energy crisis and excessive carbon emission.The Cu-based electrocatalysts have been considered for CO_(2)RR to generate hydrocarbons and alcohols.However,the application of Cu electrocatalysts has been restricted by a high onset potential for CO_(2)RR and low selectivity.In this study,we have designed a series of Cu-based single-atom alloy catalysts(SAAs),denoted as TM1/Cu(111),by doping isolated 3dtransition metal(TM)atom onto the Cu(111)surface.We theoretically evaluated their stability and investigated the activity and selectivity toward CO_(2)RR.Compared to the pure Cu catalyst,the majority TM1/Cu(111)catalysts are more favorable for hydrogenating CO_(2)and can efficiently avoid the hydrogen-evolution reaction due to the strong binding of carbonaceous intermediates.Based on the density functional theory calculations,instead of the HCOOH or CO products,the initial hydrogenation of CO_(2)on SAAs would form the*CO intermediate,which could be further hydrogenated to produce methane.In addition,we have identified the bond angle of adsorbed*CO_(2)can describe the CO_(2)activation ability of TM1/Cu(111)and the binding energy of*OH can describe the CO_(2)RR activity of TM1/Cu(111).We speculated that the V/Cu(111)can show the best activity and selectivity for CO_(2)RR among all the 3d-TM-doped TM1/Cu(111).This work could provide a rational guide to the design of new type of single-atom catalysts for efficient CO_(2)RR.展开更多
基金supported by the National Key Research and Development Project(2022YFA1503900,2022YFA1503000,and 2022YFA1203400)Shenzhen Fundamental Research Funding(JCYJ20210324115809026,JCYJ20220818100212027,and JCYJ20200109141216566)+7 种基金Shenzhen Science and Technology Program(KQTD20190929173815000)Guangdong scientific program with contract no.2019QN01L057Guangdong Innovative and Entrepreneurial Research Team Program(2019ZT08C044)to Gu Msupported by the National Natural Science Foundation of China(22033005)to Li Jpartially sponsored by Guangdong Provincial Key Laboratory of Catalysis(2020B121201002).support from Presidential fund and Development and Reform Commission of Shenzhen Municipalitysupported by the Center for Computational Science and Engineering at SUSTechthe CHEM high-performance supercomputer cluster(CHEMHPC)located at the Department of Chemistry,SUSTech。
基金the National Natural Science Foundation of China(Nos.92061109 and 22022504)Natural Science Basic Research Program of Shaanxi(Nos.2021JCW-20 and S2020-JC-WT-0001)+3 种基金Guangdong“Pearl River”Talent Plan(No.2019QN01L353)Higher Education Innovation Strong School Project of Guangdong Province of China(No.2020KTSCX122)Open Project Program of Fujian Key Laboratory of Functional Marine Sensing Materials(No.MJUKFFMSM202002)Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002).
文摘Electrochemical CO_(2)-reduction reaction(CO_(2)RR)is a promising way to alleviate energy crisis and excessive carbon emission.The Cu-based electrocatalysts have been considered for CO_(2)RR to generate hydrocarbons and alcohols.However,the application of Cu electrocatalysts has been restricted by a high onset potential for CO_(2)RR and low selectivity.In this study,we have designed a series of Cu-based single-atom alloy catalysts(SAAs),denoted as TM1/Cu(111),by doping isolated 3dtransition metal(TM)atom onto the Cu(111)surface.We theoretically evaluated their stability and investigated the activity and selectivity toward CO_(2)RR.Compared to the pure Cu catalyst,the majority TM1/Cu(111)catalysts are more favorable for hydrogenating CO_(2)and can efficiently avoid the hydrogen-evolution reaction due to the strong binding of carbonaceous intermediates.Based on the density functional theory calculations,instead of the HCOOH or CO products,the initial hydrogenation of CO_(2)on SAAs would form the*CO intermediate,which could be further hydrogenated to produce methane.In addition,we have identified the bond angle of adsorbed*CO_(2)can describe the CO_(2)activation ability of TM1/Cu(111)and the binding energy of*OH can describe the CO_(2)RR activity of TM1/Cu(111).We speculated that the V/Cu(111)can show the best activity and selectivity for CO_(2)RR among all the 3d-TM-doped TM1/Cu(111).This work could provide a rational guide to the design of new type of single-atom catalysts for efficient CO_(2)RR.
