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Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis

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Abstract

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.

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Acknowledgements

We sincerely thank Dr. Guoqiang Shen (Tianjin University) for his multitude of instructive advice on theory, logic and particulars. 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), 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).

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Authors and Affiliations

  1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

    Yingjie Zhao, Xinyue Wang, Sixing Zheng, Bin Yang, Lecheng Lei, Yang Hou & Zhongjian Li

  2. Institute of Zhejiang University-Quzhou, Quzhou, 324000, China

    Bin Yang, Lecheng Lei, Yang Hou & Zhongjian Li

  3. Nanostructure Research Centre, Wuhan University of Technology, Wuhan, 430070, China

    Xiahan Sang

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  1. Yingjie Zhao
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  2. Xinyue Wang
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Correspondence to Zhongjian Li.

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Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis

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Zhao, Y., Wang, X., Sang, X. et al. Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO2 electrolysis. Front. Chem. Sci. Eng. 16, 1772–1781 (2022). https://doi.org/10.1007/s11705-022-2197-4

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