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High-spin surface FeIV = O synthesis with molecular oxygen and pyrite for selective methane oxidation

Author

Listed:
  • Cancan Ling

    (Shanghai Jiao Tong University)

  • Meiqi Li

    (Shanghai Jiao Tong University)

  • Hao Li

    (Shanghai Jiao Tong University)

  • Xiufan Liu

    (Central China Normal University)

  • Furong Guo

    (Shanghai Jiao Tong University)

  • Yi Liu

    (Central China Normal University)

  • Rui Zhang

    (Shanghai Jiao Tong University)

  • Jincai Zhao

    (Central China Normal University)

  • Lizhi Zhang

    (Shanghai Jiao Tong University)

Abstract

Nature-inspired high-spin FeIV = O generation enables efficient ambient methane oxidation. By engineering sulfur-bridged dual ≡FeII…FeII≡ sites on pyrite (FeS2) mimicking soluble methane monooxygenase, we achieve O2-driven formation of high-spin (S = 2) surface FeIV = O species at room temperature and pressure. Strategic removal of bridging S atoms creates active sites that facilitate O2 activation via transient ≡Fe-O-O-Fe≡ intermediates, promoting homolytic O − O bond cleavage. The resulting FeIV = O exhibits an asymmetrically distorted coordination environment that reduces the crystal field splitting and favors the occupation of higher energy d-orbitals with unpaired electrons. Impressively, this configuration can efficiently convert CH4 to CH3OH through an oxygen transfer reaction with a synthetic efficiency of TOF = 27.4 h−1 and selectivity of 87.0%, outperforming most ambient O2-driven benchmarks under comparable conditions and even surpassing many H2O2-mediated systems. This study offers a facile method to synthesize high-spin surface FeIV = O and highlights the importance of metal spin state tailoring on non-enzymatic methane activation.

Suggested Citation

  • Cancan Ling & Meiqi Li & Hao Li & Xiufan Liu & Furong Guo & Yi Liu & Rui Zhang & Jincai Zhao & Lizhi Zhang, 2025. "High-spin surface FeIV = O synthesis with molecular oxygen and pyrite for selective methane oxidation," Nature Communications, Nature, vol. 16(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-63087-w
    DOI: 10.1038/s41467-025-63087-w
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