Direct oxidative carbonylation of methane to acetic acid via high-valent iron-oxo mediated water activation

Zhang, Haonan, Lewis, Richard J., Dugulan, A. Iulian, Li, Yang, Wang, Shuai, Wang, Zhenxing, Zeng, Jianrong, Dummer, Nicholas F. ORCID: https://orcid.org/0000-0002-0946-6304, Xi, Yanyan, Li, Yunyun, Davies, Thomas E., Wu, Mingbo, Hutchings, Graham J. and Wu, Wenting 2026. Direct oxidative carbonylation of methane to acetic acid via high-valent iron-oxo mediated water activation. Nature Communications 10.1038/s41467-026-70339-w

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Abstract

Direct conversion of CH4 into value-added chemicals is impeded by the inert C-H bonds and inefficient C-C coupling. We report a spatially separated Rh-O-Fe active-site architecture that decouples CH4 and H2O activation through a high-valent-metal mediated radical mechanism, enabling selective CH3COOH synthesis. In-situ infrared, operando Mössbauer spectroscopy, and quasi in-situ high-field EPR reveal that O2 oxidizes Rh and Fe to high valence states. Rh(III) activates CH4 to •CH3, while Fe(IV) = O dissociates H2O into •OH through a truncated water-gas shift pathway. •OH rapidly reacts with CO to form •COOH intermediates, which couples with •CH3 within the zeolite to yield CH3COOH. This dual-site strategy circumvents kinetic limits of conventional water-gas shift and CO insertion steps. The catalyst achieves 18.2 mmol gcat-1 h-1 CH3COOH with 92% selectivity and 100-hour stability in continuous operation. This study establishes radical decoupling enabled by high-valent metal sites as a design principle for selective alkane oxidation.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Schools > Chemistry
Publisher:	Nature Research
ISSN:	2041-1723
Date of First Compliant Deposit:	16 March 2026
Date of Acceptance:	23 February 2026
Last Modified:	16 Mar 2026 11:15
URI:	https://orca.cardiff.ac.uk/id/eprint/185763

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