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

• Published in: Nature communications Vol. 16; no. 1; pp. 7642 - 9
• Main Authors: Ling, Cancan, Li, Meiqi, Li, Hao, Liu, Xiufan, Guo, Furong, Liu, Yi, Zhang, Rui, Zhao, Jincai, Zhang, Lizhi
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 16.08.2025; Nature Publishing Group; Nature Portfolio
• Subjects: 639/638/224/685; 639/638/77/884; 639/638/77/885; 639/638/77/887; Adsorption; Benchmarks; Chemical synthesis; Electrons; Energy; Geometry; Humanities and Social Sciences; Hydrogen peroxide; Intermediates; Iron; Iron sulfides; Ligands; Methane; Methane monooxygenase; multidisciplinary; Oxidation; Oxygen transfer; Pyrite; Room temperature; Science; Science (multidisciplinary); Selectivity; Soluble methane monooxygenase; Sulfur; Symmetry
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-025-63087-w

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