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

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

Nature Communications, 2025, vol. 16, issue 1, 1-9

Abstract: 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.

Date: 2025
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DOI: 10.1038/s41467-025-63087-w

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