Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis
Yingjie Zhao , Xinyue Wang , Xiahan Sang , Sixing Zheng , Bin Yang , Lecheng Lei , Yang Hou , Zhongjian Li
Front. Chem. Sci. Eng. ›› 2022, Vol. 16 ›› Issue (12) : 1772 -1781.
Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis
Unlocking of the extremely inert C=O bond during electrochemical CO2 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.
CO2 electrolysis / single-atom catalysts / spin polarization / proton dynamics / in situ IR spectroscopy / kinetic isotope effect
Higher Education Press
Supplementary files
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