Atomic Dispersed Hetero‑Pairs for Enhanced Electrocatalytic CO_(2)Reduction  

作　　者：Zhaoyong Jin Meiqi Yang Yilong Dong Xingcheng Ma Ying Wang Jiandong Wu Jinchang Fan Dewen Wang Rongshen Xi Xiao Zhao Tianyi Xu Jingxiang Zhao Lei Zhang David J.Singh Weitao Zheng Xiaoqiang Cui 

机构地区：[1]State Key Laboratory of Automotive Simulation and Control,School of Materials Science and Engineering,Key Laboratory of Automobile Materials of MOE,Electron Microscopy Center,Jilin University,Changchun 130012,People’s Republic of China [2]Key Laboratory of Photonic and Electronic Bandgap Materials,Ministry of Education,and College of Chemistry and Chemical Engineering,Harbin Normal University,Harbin 150025,People’s Republic of China [3]College of Chemistry,Jilin University,Changchun 130012,People’s Republic of China [4]Department of Physics and Astronomy and Department of Chemistry,University of Missouri,Columbia,MO 65211,USA

出　　处：《Nano-Micro Letters》2024年第1期55-67,共13页纳微快报（英文版）

基　　金：the National Natural Science Foundation of China(22279044,12034002,and 22202080);the Project for Self-Innovation Capability Construction of Jilin Province Development and Reform Commission(2021C026);Jilin Province Science and Technology Development Program(20210301009GX);the Fundamental Research Funds for the Central Universities.

摘　　要：Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

关 键 词：CO_(2)reduction reaction Atomic dispersed catalyst Hetero-diatomic pair Ad-desorption energy Linear scaling relation 

分 类 号：O64[理学—物理化学]