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Robust Fe-N4-C6O2 single atom sites for efficient PMS activation and enhanced FeIV = O reactivity

Author

Listed:
  • Tiantian Chen

    (Central China Normal University)

  • Ganbing Zhang

    (Hubei University)

  • Hongwei Sun

    (Central China Normal University)

  • Yetong Hua

    (Central China Normal University)

  • Shu Yang

    (Central China Normal University)

  • Dandan Zhou

    (Central China Normal University)

  • Haoxin Di

    (Central China Normal University)

  • Yiling Xiong

    (Central China Normal University)

  • Shenghuai Hou

    (Central China Normal University)

  • Hui Xu

    (Central China Normal University)

  • Lizhi Zhang

    (Shanghai Jiao Tong University)

Abstract

The microenvironment regulation of Fe-N4 single atom catalysts (SACs) critically governs peroxymonosulfate (PMS) activation. Although conventional heteroatom substitution in primary coordination enhances activity, it disrupts Fe-N4 symmetry and compromises stability. Herein, we propose oxygen doping in the secondary coordination shell to construct Fe-N4-C6O2 SAC, which amplifies the localized electric field while preserving the pristine coordination symmetry, thus trading off its activity and stability. This approach suppresses Fe-N bond structural deformation (bond amplitude reduced from 0.875–3.175 Å to 0.925–2.975 Å) during PMS activation by lowering Fe center electron density to strengthen Fe-N bond, achieving extended catalytic durability (>240 h). Simultaneously, the weakened coordination field lowers the Fe=O σ* orbital energy, promoting electrophilic σ-attack of high-valent iron-oxo towards bisphenol A, and increasing its degradation rate by 41.6-fold. This work demonstrates secondary coordination engineering as a viable strategy to resolve the activity-stability trade-off in SAC design, offering promising perspectives for developing environmental catalysts.

Suggested Citation

  • Tiantian Chen & Ganbing Zhang & Hongwei Sun & Yetong Hua & Shu Yang & Dandan Zhou & Haoxin Di & Yiling Xiong & Shenghuai Hou & Hui Xu & Lizhi Zhang, 2025. "Robust Fe-N4-C6O2 single atom sites for efficient PMS activation and enhanced FeIV = O reactivity," Nature Communications, Nature, vol. 16(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57643-7
    DOI: 10.1038/s41467-025-57643-7
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    1. Yuan Pan & Yinjuan Chen & Konglin Wu & Zheng Chen & Shoujie Liu & Xing Cao & Weng-Chon Cheong & Tao Meng & Jun Luo & Lirong Zheng & Chenguang Liu & Dingsheng Wang & Qing Peng & Jun Li & Chen Chen, 2019. "Regulating the coordination structure of single-atom Fe-NxCy catalytic sites for benzene oxidation," Nature Communications, Nature, vol. 10(1), pages 1-11, December.
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