Elucidating the fundamental mechanisms underlying Cu reconstruction is paramount for the rational design of catalysts that meet the stringent activity,selectivity,and durability requirements for industrial-scale CO_(2...Elucidating the fundamental mechanisms underlying Cu reconstruction is paramount for the rational design of catalysts that meet the stringent activity,selectivity,and durability requirements for industrial-scale CO_(2)/CO electroreduction(CO_(2)RR/CORR).While both dissolution-redeposition and atomic migration pathways have been proposed,the operational conditions dictating their relative dominance remain poorly understood.Through quasi in situ Cu^(+)detection and in situ atomic force microscopy(AFM),we reveal a striking mechanistic dichotomy:Cu reconstruction during CO_(2)RR occurs strictly in the presence of Cu^(+),whereas CORR-induced reconstruction proceeds independently of Cu^(+)species.These findings suggest that Cu reconstruction in CO_(2)RR follows a dissolution-redeposition mechanism induced by oxidative radicals,while atomic migration emerges as the dominant pathway in CORR.Density functional theory calculations further demonstrate that adsorbed*CO intermediates reduce Cu-Cu bond strength,creating metastable surface configurations that promote Cu atomic migration.These insights provide a foundation for leveraging reconstruction to design high-performance Cu-based catalysts.展开更多
基金supported by the National Natural Science Foundation of China(52471235 and 51972223)the National Industry-Education Platform for Energy Storage(Tianjin University)the Fundamental Research Funds for the Central Universities,and the Haihe Laboratory of Sustainable Chemical.
文摘Elucidating the fundamental mechanisms underlying Cu reconstruction is paramount for the rational design of catalysts that meet the stringent activity,selectivity,and durability requirements for industrial-scale CO_(2)/CO electroreduction(CO_(2)RR/CORR).While both dissolution-redeposition and atomic migration pathways have been proposed,the operational conditions dictating their relative dominance remain poorly understood.Through quasi in situ Cu^(+)detection and in situ atomic force microscopy(AFM),we reveal a striking mechanistic dichotomy:Cu reconstruction during CO_(2)RR occurs strictly in the presence of Cu^(+),whereas CORR-induced reconstruction proceeds independently of Cu^(+)species.These findings suggest that Cu reconstruction in CO_(2)RR follows a dissolution-redeposition mechanism induced by oxidative radicals,while atomic migration emerges as the dominant pathway in CORR.Density functional theory calculations further demonstrate that adsorbed*CO intermediates reduce Cu-Cu bond strength,creating metastable surface configurations that promote Cu atomic migration.These insights provide a foundation for leveraging reconstruction to design high-performance Cu-based catalysts.
