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<p>Nature-inspired high-spin Fe<sup>IV</sup> = O generation enables efficient ambient methane oxidation. By engineering sulfur-bridged dual ≡Fe<sup>II</sup>…Fe<sup>II</sup>≡ sites on pyrite (FeS<sub>2</sub>) mimicking soluble methane monooxygenase, we achieve O<sub>2</sub>-driven formation of high-spin (S = 2) surface Fe<sup>IV</sup> = O species at room temperature and pressure. Strategic removal of bridging S atoms creates active sites that facilitate O<sub>2</sub> activation via transient ≡Fe-O-O-Fe≡ intermediates, promoting homolytic O − O bond cleavage. The resulting Fe<sup>IV</sup> = 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 CH<sub>4</sub> to CH<sub>3</sub>OH through an oxygen transfer reaction with a synthetic efficiency of TOF = 27.4 h<sup>−1</sup> and selectivity of 87.0%, outperforming most ambient O<sub>2</sub>-driven benchmarks under comparable conditions and even surpassing many H<sub>2</sub>O<sub>2</sub>-mediated systems. This study offers a facile method to synthesize high-spin surface Fe<sup>IV</sup> = O and highlights the importance of metal spin state tailoring on non-enzymatic methane activation.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年8月16日

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  • Cancan Ling,
  • Meiqi Li,
  • Hao Li,
  • Xiufan Liu,
  • Furong Guo,
  • Yi Liu,
  • Rui Zhang,
  • Jincai Zhao,
  • Lizhi Zhang

摘要

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.