Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)acc...Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22479097)the Shanghai Science and Technology Committee(Grant No.23ZR1433000)the National High-Level Talent Program for Young Scholars,the Start-up Fund(F.S.)from Shanghai Jiao Tong University.
文摘Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
