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Sulfur-doping tunes p-d orbital coupling over asymmetric Zn-Sn dual-atom for boosting CO2 electroreduction to formate

Author

Listed:
  • Bo Peng

    (Beijing Institute of Technology
    Guangxi Minzu University)

  • Hao She

    (Jiangsu University)

  • Zihao Wei

    (Beijing Institute of Technology)

  • Zhiyi Sun

    (Beijing Institute of Technology)

  • Ziwei Deng

    (Beijing Institute of Technology)

  • Zhongti Sun

    (Jiangsu University)

  • Wenxing Chen

    (Beijing Institute of Technology)

Abstract

The interaction of p-d orbitals at bimetallic sites plays a crucial role in determining the catalytic reactivity, which facilitates the modulation of charges and enhances the efficiency of CO2 electroreduction process. Here, we show a ligand co-etching approach to create asymmetric Zn-Sn dual-atom sites (DASs) within metal-organic framework (MOF)-derived yolk-shell carbon frameworks (named Zn1Sn1/SNC). The DASs comprise one Sn center (p-block) partially doped with sulfur and one Zn center (d-block) with N coordination, facilitating the coupling of p-d orbitals between the Zn-Sn dimer. The N-Zn-Sn-S/N arrangement displays an asymmetric distribution of charges and atoms, leading to a stable adsorption configuration of HCOO* intermediates. In H-type cell, Zn1Sn1/SNC exhibits an impressive formate Faraday efficiency of 94.6% at -0.84 V. In flow cell, the asymmetric electronic architecture of Zn1Sn1/SNC facilitates high accessibility, leading to a high current density of -315.2 mA cm-2 at -0.90 V. Theoretical calculations show the asymmetric sites in Zn1Sn1/SNC with ideal adsorption affinity lower the CO2 reduction barrier, thus improve the overall efficiency of CO2 reduction.

Suggested Citation

  • Bo Peng & Hao She & Zihao Wei & Zhiyi Sun & Ziwei Deng & Zhongti Sun & Wenxing Chen, 2025. "Sulfur-doping tunes p-d orbital coupling over asymmetric Zn-Sn dual-atom for boosting CO2 electroreduction to formate," Nature Communications, Nature, vol. 16(1), pages 1-11, December.
  • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57573-4
    DOI: 10.1038/s41467-025-57573-4
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