锡掺杂稳定残留氧促进中间体解吸以增强CO_(2)向CO转化  

Sn-doping stabilizes residual oxygen species to promote intermediate desorption for enhanced CO_(2) to CO conversion

作　　者：闫春柳 袁惠敏 王鑫阳 郝睿 刘桂雨 罗文 王志强 刘昆 王振宇 兰阳春 崔德虎 卢周广 Chunliu Yan;Huimin Yuan;Xinyang Wang;Rui Hao;Guiyu Liu;Wen Luo;Zhiqiang Wang;Kun Liu;Zhenyu Wang;Yangchun Lan;Dehu Cui;Zhouguang Lu(Department of Materials Science and Engineering,Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials,Southern University of Science and Technology,Shenzhen 518055,China;School of Microelectronics,Southern University of Science and Technology,Shenzhen 518055,China)

机构地区：[1]Department of Materials Science and Engineering,Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials,Southern University of Science and Technology,Shenzhen 518055,China [2]School of Microelectronics,Southern University of Science and Technology,Shenzhen 518055,China

出　　处：《Science China Materials》2023年第9期3547-3554,共8页中国科学（材料科学（英文版）

基　　金：supported by Shenzhen Science and Technology Foundation of Nanshan (K20799112);the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20200109141640095);the National Natural Science Foundation of China (21875097);Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials (ZDSYS20200421111401738);supported by the National Supercomputer Center in Guangzhou;the National Supercomputing Center in Shenzhen (Shenzhen Cloud Computing Center);the Center for Computational Science and Engineering at SUSTech。

摘　　要：铜基氧化物表面的氧化物种可以增强CO_(2)吸附,降低含氧中间体的结合能,从而提高电还原CO_(2)的一步还原产物的产率.鉴于此,在还原过程中,Cu_(2)O上的残留氧通过Sn^(2+)稳定,并且残留氧的保留通过原位拉曼光谱(Cu–O_(ads))得到了证实.同时,原位拉曼光谱和密度泛函理论计算结果证明,由于残留氧的存在,一氧化碳中间体在SnO/Cu_(2)O催化剂的吸附能比Cu_(2)O催化剂明显降低.这使得其在-0.8 V (相对于可逆氢电极)的电位下获得高达97.5%的法拉第效率.铜基氧化物催化剂的氧稳定策略对设计高性能电还原CO_(2)催化剂具有指导意义.The presence of oxygen species on the surface of Cu oxides can improve carbon dioxide(CO_(2))adsorption and lower the binding energy of oxygenic intermediates,thereby increasing the first-step reduction products of CO_(2) electroreduction.Herein,the residual oxygen on Cu_(2)O was stabilized using Sn^(2+)during the reduction process,and the retention of residual oxygen was confirmed using an in-situ Raman spectrum(Cu–O_(ads)).Simultaneously,in-situ Raman and density functional theory calculations revealed that the adsorption energy of carbon monoxide intermediate(*CO)on SnO/Cu_(2)O catalyst was considerably lower than that on bare Cu_(2)O catalyst due to the presence of residual oxygen.This resulted in an increased Faradic efficiency of 97.5%for CO production at a relevant potential of−0.8 V(vs.reversible hydrogen electrode).The oxygen stabilizing strategy for Cu oxide catalysts is inspiring in designing high-performance catalysts for CO_(2) electroreduction.

关 键 词：氧化物催化剂 密度泛函理论计算 电还原 还原产物 原位拉曼光谱 一氧化碳 氢电极 结合能 

分 类 号：TQ426[化学工程] TQ127.1