Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splittin...Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splitting,which is still challenging for developing efficient single-atom catalysts limited by their structural simplicity usually incompetent to handle this task.Incorporation of extra functional units should be viable.Herein,a proton deployment strategy is demonstrated via“atomic and nanostructured iron(A/N-Fe)pairs”,comprising atomically dispersed iron active centers spin-polarized by nanostructured iron carbide ferromagnets,to boost the critical protonation steps.The as-designed catalyst displays a broad window(300 mV)for CO selectivity>90%(98%maximum),even outperforming numerous cutting-edge M–N–C systems.The well-placed control of proton dynamics by A/N-Fe can promote*COOH/*CO formation and simultaneously suppress H2 evolution,benefiting from the magnetic-proximity-induced exchange splitting(spin polarization)that properly adjusts energy levels of the Fe sites’d-shells,and further those of the adsorbed intermediates’antibonding molecular orbitals.展开更多
基金This work was financially supported by National Natural Science Foundation of China(Grant Nos.22075245,21922811,21878270,and 21961160742)Zhejiang Provincial Natural Science Foundation of China(Grant No.LR19B060002)+2 种基金Fundamental Research Funds for the Central Universities(Grant No.2020XZZX002-09)Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(Grant No.2019R01006)Startup Foundation for Hundred-Talent Program of Zhejiang University,Key Laboratory of Marine Materials and Related Technologies,Chinese Academy of Science,and Zhejiang Key Laboratory of Marine Materials and Protective Technologies(2020K10).
文摘Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splitting,which is still challenging for developing efficient single-atom catalysts limited by their structural simplicity usually incompetent to handle this task.Incorporation of extra functional units should be viable.Herein,a proton deployment strategy is demonstrated via“atomic and nanostructured iron(A/N-Fe)pairs”,comprising atomically dispersed iron active centers spin-polarized by nanostructured iron carbide ferromagnets,to boost the critical protonation steps.The as-designed catalyst displays a broad window(300 mV)for CO selectivity>90%(98%maximum),even outperforming numerous cutting-edge M–N–C systems.The well-placed control of proton dynamics by A/N-Fe can promote*COOH/*CO formation and simultaneously suppress H2 evolution,benefiting from the magnetic-proximity-induced exchange splitting(spin polarization)that properly adjusts energy levels of the Fe sites’d-shells,and further those of the adsorbed intermediates’antibonding molecular orbitals.
