Constructing a high-efficiency composite material for CO_(2)photoreduction is a key step to the achievement of carbon neutralization,but a comprehensive understanding of the factors that dictate CO_(2)reduction activi...Constructing a high-efficiency composite material for CO_(2)photoreduction is a key step to the achievement of carbon neutralization,but a comprehensive understanding of the factors that dictate CO_(2)reduction activity remains elusive.Here,we constructed a series of Cu in situ combined on Cu_(2)O(Cu/Cu_(2)O-1,-2,-3)via an acid disproportionation method with various processing time.The optimal photocatalyst(Cu/Cu_(2)O-2)affords CO at a rate of 10.43μmol·g^(−1)·h^(−1),which is more than fourfold to that of pristine Cu_(2)O.Electron transfer in the samples was detected by X-ray absorption spectroscopy(XAS)as well as X-ray photoelectron spectroscopy(XPS).Interestingly,the best photoreduction performance was not achieved by the sample possessing the most electron transfer(Cu/Cu_(2)O-1)but by the one with moderate electron transfer(Cu/Cu_(2)O-2).By virtue of density functional theory(DFT)calculations,a linear relationship between Bader charge variation(Δq)of the active sites and adsorption energy of CO_(2)reduction intermediates was discovered,wherein the moderate charge transfer corresponds to appropriate adsorption energy,which benefits CO_(2)photoreduction activity substantially.This work provides guidance for the construction of composite catalysts for efficient CO_(2)photoreduction in a perspective of the quantity of electron transfer.展开更多
基金the Key Research and Development of Ministry of Science and Technology of China(No.2021YFF0500502)the National Natural Science Foundation of China(NSFC,Nos.22090044,21831003,21621001,and 91959201)+1 种基金the Jilin Province Science and Technology Development Plan(Nos.20200802003GH,20200801005GH and 20210509035RQ)Users with Excellence Program of Hefei Science Center,Chinese Academy of Sciences(CAS)(No.2020HSC-UE002).
文摘Constructing a high-efficiency composite material for CO_(2)photoreduction is a key step to the achievement of carbon neutralization,but a comprehensive understanding of the factors that dictate CO_(2)reduction activity remains elusive.Here,we constructed a series of Cu in situ combined on Cu_(2)O(Cu/Cu_(2)O-1,-2,-3)via an acid disproportionation method with various processing time.The optimal photocatalyst(Cu/Cu_(2)O-2)affords CO at a rate of 10.43μmol·g^(−1)·h^(−1),which is more than fourfold to that of pristine Cu_(2)O.Electron transfer in the samples was detected by X-ray absorption spectroscopy(XAS)as well as X-ray photoelectron spectroscopy(XPS).Interestingly,the best photoreduction performance was not achieved by the sample possessing the most electron transfer(Cu/Cu_(2)O-1)but by the one with moderate electron transfer(Cu/Cu_(2)O-2).By virtue of density functional theory(DFT)calculations,a linear relationship between Bader charge variation(Δq)of the active sites and adsorption energy of CO_(2)reduction intermediates was discovered,wherein the moderate charge transfer corresponds to appropriate adsorption energy,which benefits CO_(2)photoreduction activity substantially.This work provides guidance for the construction of composite catalysts for efficient CO_(2)photoreduction in a perspective of the quantity of electron transfer.
