Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis
Yingjie Zhao1, Xinyue Wang1, Xiahan Sang3, Sixing Zheng1, Bin Yang1,2, Lecheng Lei1,2, Yang Hou1,2, Zhongjian Li1,2()
1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China 2. Institute of Zhejiang University-Quzhou, Quzhou 324000, China 3. Nanostructure Research Centre, Wuhan University of Technology, Wuhan 430070, China
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.
. [J]. Frontiers of Chemical Science and Engineering, 2022, 16(12): 1772-1781.
Yingjie Zhao, Xinyue Wang, Xiahan Sang, Sixing Zheng, Bin Yang, Lecheng Lei, Yang Hou, Zhongjian Li. Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis. Front. Chem. Sci. Eng., 2022, 16(12): 1772-1781.
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