Shaping hollow spherical assemblies for enhanced Cu^(0)/Cu^(+) interface to boost C_(2+) selectivity in CO_(2) electroreduction  

中空球形组装体强化Cu^(0)/Cu^(+)界面促进CO_(2)电催化还原为C_(2+)产物

作　　者：Yu Li Haojun Shi Congcong Li Zhongliang Liu Weizheng Tang Tingting Zhang Shixin Yin Huihui Li Chunzhong Li 黎雨;史皓峻;李聪聪;刘忠梁;唐玮峥;张婷婷;阴世新;李会会;李春忠(Key Laboratory for Ultrafine Materials of Ministry of Education,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]Key Laboratory for Ultrafine Materials of Ministry of Education,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China [2]Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China

出　　处：《Science China Materials》2024年第11期3596-3601,共6页中国科学（材料科学）（英文版）

基　　金：supported by the National Natural Science Foundation of China(21838003,21771170,22008069);the Shanghai Municipal Science and Technology Major Project;the Fundamental Research Funds for the Central Universities(JKD01241702);the Shanghai Rising-Star Program(20QA1402700)。

摘　　要：The creation of Cu^(0)/Cu^(+)interface over Cubased catalysts is known to facilitate the production of multicarbon(C_(2+))products during CO_(2)reduction reaction(CO_(2)RR).However,the Cu^(+)moieties exhibit high susceptibility towards reduction into Cu^(0)at a high current density.Thus,a comprehensive understanding and rational shaping strategy for the construction and stabilization of Cu^(0)/Cu^(+)interface in Cu-based catalysts is imperative.Herein,we proposed a controllable“nanoparticle assembly”strategy to obtain hollow spherical assemblies(HSA)composed of numerous Cu_(2)O nanoparticles(HSA-Cu_(2)O).The HSA-Cu_(2)O catalysts significantly enhance the selectivity of C_(2+)products,resulting in an impressive overall Faraday efficiency(FE)of 79.2%±0.7%at a partial current density of 317.1 mA cm−2.The HSA-Cu_(2)O catalysts undergo in-situ electrochemically reconstruction during CO_(2)RR,achieving Cu^(0)/Cu^(+)interfacial sites with a high density.The Auger electron spectra,in-situ Raman,and morphological evolution studies have confirmed that the combination of the Cu^(0)/Cu^(+)interface and hollow sphere architecture facilitated the concentration of*CO intermediates,thereby promoting C–C dimerization to boost C_(2+)selectivity in CO_(2)RR.在铜基催化剂表面构建Cu^(0)/Cu^(+)界面有利于电催化CO_(2)还原(CO_(2)RR)为多碳(C_(2+))产物.然而,在高电流密度下,Cu^(+)物种很容易被还原成金属Cu.因此,深入理解并合理设计和构建Cu基催化剂表面Cu^(0)/Cu^(+)界面对提高C_(2+)产物选择性具有重要的意义.基于此,我们提出了一种可控的“纳米粒子组装”策略,以获得由大量Cu_(2)O纳米粒子组成的中空球形组装体(HSA-Cu_(2)O).HSA-Cu_(2)O催化剂显著提高了C_(2+)产物的选择性,其法拉第效率(FE)达到了79.2%±0.7%,C_(2+)产物的部分电流密度为317.1 mA cm^(-2).在CO_(2)RR过程中,HSA-Cu_(2)O催化剂发生了原位电化学重构,实现了高密度的Cu^(0)/Cu^(+)活性界面位点的构建.俄歇电子能谱、原位拉曼和结构演变过程研究证实,Cu^(0)/Cu^(+)界面与中空球限域结构的结合促进了~*CO中间体的富集,从而促进了~*CO二聚化,提高了CO_(2)RR中C_(2+)产物的选择性.

关 键 词：Cu^(0)/Cu^(+) interface hollow spherical assemblies confinement effect C-C coupling 

分 类 号：X701[环境科学与工程—环境工程] TQ21[化学工程—有机化工] O643.36[理学—物理化学]