Single-site metal atoms or clusters(SMCs)present high potential to enable the exploration of energetics and kinetics in heterogeneous photocatalysis owing to their unique properties.Here,we report the first work for highly no ligands-protected atomic-level Cu clusters by mediating them in Cd vacancies at the edge of CdS nanorods(CuCR SCC)towards photocatalytic CO2 conversion.X-ray absorption spectromet-ric analysis and photoelectric dynamic characterizations demonstrate that the well-defined Cu clusters across the Cd vacancies induce a synergistic effect on CO2 reduction through the interfacial conjunction,accelerating charge carrier mobility and facilitating atom utilization.In situ diffuse reflectance infrared Fourier transform spectroscopy,low-coverage calculated isosteric heat,and theoretical studies unveil that the direct cluster/substrate conjunction provides a driving force for interfacial electronic modification and dynamic cooperation.Besides,Cu acts as the active site in the process of CO2 photoreduction,which en-hances the adsorption and activation of CO2.Consequently,this leads to outstanding CO2-to-CO conver-sion with a turnover number of more than 90 without the addition of any sacrificial agent.Particularly,the Cu clusters-mediated CdS nanorods are able to serve as carrier provider,allowing the photogenerated electrons transfer from CdS to Cu clusters.These electrons received from CdS can further enhance the charge carrier separation and thus achieve high photostability during longtime light irradiation.

Lei Cheng;Baihai Li;Hui Yin;Jiajie Fan;Quanjun Xiang

State Key Laboratory of Electronic Thin Film and Integrated Devices,School of Electronic Science and Engineering,University of Electronic Science and Technology of China,Chengdu 610054,China;Yangtze Delta Region Institute(Huzhou),University of Electronic Science and Technology of China,Huzhou 313001,China;School of Materials and Energy,University of Electronic Science and Technology of China,Chengdu 610054,China;College of Resources and Environment,Huazhong Agricultural University,Wuhan 430070,China;School of Materials Science and Engineering,Zhengzhou University,Zhengzhou 450002,China

材料科学技术（英文版）

[1]Lei Cheng;Baihai Li;Hui Yin;Jiajie Fan;Quanjun Xiang-.Cu clusters immobilized on Cd-defective cadmium sulfide nano-rods towards photocatalytic CO2 reduction)[J].材料科学技术（英文版）,2022(23):54-63

CuCR,spectromet,longtime

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