Mechanistic investigation on Ag-Cu_(2)O in electrocatalytic CO_(2) to CH_(4) by in situ/operando spectroscopic and theoretical analysis  

作　　者：Min Sun Luxiao Zhang Fuli Tian Jiaxin Li Yanqiu Lei Heng Zhang Lifeng Han Zhihua Guo Yonghui Gao Fenrong Liu Yan Wang Luhui Wang Shanghong Zeng 

机构地区：[1]School of Chemistry and Chemical Engineering,Inner Mongolia University,Hohhot 010021,Inner Mongolia,China [2]Key Laboratory of Medicinal and Edible Plants Resources of Hainan Province,Hainan Vocational University of Science and Technology,Haikou 571126,Hainan,China [3]State Key Laboratory of Baiyunobo Rare Earth Resource Research and Comprehensive Utilization,Baotou Research Institute of Rare Earths,Baotou 014030,Inner Mongolia,China [4]Zhejiang Key Laboratory of Petrochemical Environmental Pollution Control,Zhejiang Ocean University,Zhoushan 316022,Zhejiang,China

出　　处：《Journal of Energy Chemistry》2024年第1期521-531,I0012,共12页能源化学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (21968020);the Natural Science Foundation of Inner Mongolia (2022MS02011 and 2023MS02014);the Science and Technology Projects of China Northern Rare Earth (BFXT-2022-D-0023);the Open Research Subject of Zhejiang Key Laboratory of Petrochemical Environmental Pollution Control (2021Z01)。

摘　　要：Silver-copper electrocatalysts have demonstrated effectively catalytic performance in electroreduction CO_(2) toward CH_(4),yet a revealing insight into the reaction pathway and mechanism has remained elusive.Herein,we construct chemically bonded Ag-Cu_(2)O boundaries,in which the complete reduction of Cu_(2)O to Cu has been strongly impeded owing to the presence of surface Ag shell.The interfacial confinement effect helps to maintain Cu^(+)sites at the Ag-Cu_(2)O boundaries.Using in situ/operando spectroscopy and theoretical simulations,it is revealed that CO_(2) is enriched at the Ag-Cu_(2)O boundaries due to the enhanced physisorption and chemisorption to CO_(2),activating CO_(2) to form the stable intermediate^(*)CO.The boundaries between Ag shell and the Cu_(2)O mediate local^(*)CO coverage and promote^(*)CHO intermediate formation,consequently facilitating CO_(2)-to-CH_(4) conversion.This work not only reveals the structure-activity relationships but also offers insights into the reaction mechanism on Ag-Cu catalysts for efficient electrocatalytic CO_(2) reduction.

关 键 词：Ag shell Interfacial confinement effect Cu~+ Local*CO coverage CO_(2)reduction 

分 类 号：O643.36[理学—物理化学] TQ221.11[理学—化学]