Electron transfer in Cu/Cu_(2)O generated by disproportionation promoting efficient CO_(2)photoreduction  

作　　者：Qian Zhu Kainan Zhu Minmin Cai Yaowen Zhang Zhiyu Shao Mengpei Jiang Xiyang Wang Zhibin Geng Xiaofeng Wu Manrong Li Keke Huang Shouhua Feng 

机构地区：[1]State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials College of Chemistry,Jilin University,Changchun 130012,China [2]Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275,China

出　　处：《Nano Research》2022年第8期7099-7106,共8页纳米研究（英文版）

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);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).

摘　　要：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.

关 键 词：CO_(2)photocatalytic conversion charge transfer composite density functional theory(DFT) 

分 类 号：O64[理学—物理化学]