Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO<sub>2</sub> electrolysis

doi:10.1007/s11705-022-2197-4

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (12) : 1772-1781 https://doi.org/10.1007/s11705-022-2197-4

RESEARCH ARTICLE

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 Yang^1,², Lecheng Lei^1,², Yang Hou^1,², Zhongjian Li^1,²(

)

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

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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.

Keywords CO₂ electrolysis single-atom catalysts spin polarization proton dynamics in situ IR spectroscopy kinetic isotope effect

Corresponding Author(s): Zhongjian Li

Online First Date: 14 October 2022 Issue Date: 19 December 2022

Cite this article:

Yingjie Zhao,Xinyue Wang,Xiahan Sang, et al. Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO₂ electrolysis[J]. Front. Chem. Sci. Eng., 2022, 16(12): 1772-1781.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2197-4
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I12/1772

Fig.1 Synthetic route of Fe₃C-X@Fe-NC.

Fig.2 Theoretical analysis of electronic structure and reaction path for SA-Fe and A/N-Fe. (a) Transport of the proximity-induced spin polarization by Fe₃C ferromagnet into anchored Fe site. (b) LDOS profiles projected on Fe 3d of the catalytic Fe sites; vertical dashed lines: d-band centers. (c) Exchange splitting that alters electron spins and energy levels of the entire system. (d) Metal-intermediate bond formation. (e) Changes in structural geometry and molecular orbital energies of a CO₂-relevant intermediate when accepting the spin-polarized carriers from the magnetic Fe site. (f) LDOS projected onto Fe 3d of the atomic Fe site and C & O 2p of the adsorbed COOH intermediate in (SA-Fe)–*COOH and (A/N-Fe)–*COOH. Free energy diagrams of (g) CO₂RR and (h) HER.

Fig.3 Physical characterizations for Fe₃C-L@Fe-NC. (a) TEM image; (b) HRTEM image; insets: index crystal planes of graphite (top-right) and Fe₃C (bottom-left); (c) XRD spectrum; (d) EDS elemental mapping images; (e) AC-HAADF-STEM image; (f) XPS N 1s spectrum.

Fig.4 Electrochemical CO₂RR performances of Fe₃C-X@Fe-NCs and Fe-NC. (a) FE_CO; (b) J_CO; (c) TOFs; (d) optimal FE_CO of Fe₃C-L@Fe-NC in comparison with other carbon-supported non-precious TM-N SACs; (e) long-term chronoamperometry curve and time-dependent FE_CO plot of Fe₃C-L@Fe-NC at –0.50 V.

Fig.5 Analysis of CO₂RR kinetics via in situ ATR-SEIRAS spectra.

Fig.6 KIE evaluations on CO₂RR and HER in protic and deuterated electrolytes. (a) FE of CO and H₂/D₂; (b) H₂/D₂ formation rates with the corresponding KIE values; (c) CO formation rates under different proton conditions.

Fig.7 Proposed mechanism of the proton dynamics optimized by A/N-Fe during CO₂ electrolysis.

Fig.8 Device performances of the assembled ZCBs. (a) Schematic of a ZCB. (b) Discharge and charge polarization curves; inset: power density profiles. (c) FE_CO upon ZCB discharging at varying constant-currents. (d) Digital photograph of an LED array lighted up by Fe₃C-L@Fe-NC–equipped ZCBs in serial connection. (e) Galvanostatic discharge/charge cycling curves at 1.0 mA·cm^–2.

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