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 h...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 Cd S nanorods(Cu CR SCC)towards photocatalytic CO_(2)conversion.X-ray absorption spectrometric analysis and photoelectric dynamic characterizations demonstrate that the well-defined Cu clusters across the Cd vacancies induce a synergistic effect on CO_(2)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 CO_(2)photoreduction,which enhances the adsorption and activation of CO_(2).Consequently,this leads to outstanding CO_(2)-to-CO conversion with a turnover number of more than 90 without the addition of any sacrificial agent.Particularly,the Cu clusters-mediated Cd S nanorods are able to serve as carrier provider,allowing the photogenerated electrons transfer from Cd S to Cu clusters.These electrons received from Cd S can further enhance the charge carrier separation and thus achieve high photostability during longtime light irradiation.展开更多
基金supported by the National Natural Science Foundation of China(Nos.51672099 and 52073263)the Sichuan Science and Technology Program under(No.2021JDTD0026)the Fundamental Research Funds for the Central Universities(Nos.2017-QR-25 and ZYGX2019J031)。
文摘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 Cd S nanorods(Cu CR SCC)towards photocatalytic CO_(2)conversion.X-ray absorption spectrometric analysis and photoelectric dynamic characterizations demonstrate that the well-defined Cu clusters across the Cd vacancies induce a synergistic effect on CO_(2)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 CO_(2)photoreduction,which enhances the adsorption and activation of CO_(2).Consequently,this leads to outstanding CO_(2)-to-CO conversion with a turnover number of more than 90 without the addition of any sacrificial agent.Particularly,the Cu clusters-mediated Cd S nanorods are able to serve as carrier provider,allowing the photogenerated electrons transfer from Cd S to Cu clusters.These electrons received from Cd S can further enhance the charge carrier separation and thus achieve high photostability during longtime light irradiation.
