Subnanometric MoO<sub>x</sub> clusters limit overoxidation during photocatalytic CH<sub>4</sub> conversion to oxygenates over TiO<sub>2</sub>.

Wu, Panpan; Chu, Yueying; Wang, Maoling; Feng, Ningdong; Xu, Jun; Ma, Ding; Ye, Jinhua; Deng, Feng · Nat Commun · 2025

basic_science · Level V

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Abstract

Direct photocatalytic oxidation of methane to high-value-added oxygenated products remains a great challenge due to the unavoidable overoxidation of target products. Here, we report an efficient and highly selective TiO<sub>2</sub> photocatalyst anchored with subnanometric MoO<sub>x</sub> clusters for photocatalytic methane oxidation to organic oxygenates by oxygen. A high organic oxygenates yield of 3.8 mmol/g with nearly 100% selectivity was achieved after 2 h of light irradiation, resulting in a 13.3% apparent quantum yield at 365 nm. Mechanistic studies reveal a photocatalytic cycle for methane oxidation on the MoO<sub>x</sub> anchored TiO<sub>2</sub>, which not only largely inhibits the formation of hydroxyl and superoxide radicals and the overoxidation of oxygenate products but also facilitates the activation of the first carbon-hydrogen bond of methane. This work would promote the rational design of efficient non-noble metal catalysts for direct conversion of methane to high-value-added oxygenates.