Iron Oxide Clusters as Electron Donors Under Light Enhance Oxygen Reduction Kinetics at Atomically Dispersed Fe for Photocatalytic CH4 Partial Oxidation

Abstract Photocatalytic CH 4 oxidation to CH 3 OH emerges as a promising strategy to sustainably utilize natural gas and mitigate the greenhouse effect. However, there remains a significant challenge for the synthesis of methanol by using O 2 at low temperature. Inspired by the catalytic structure in soluble methane monooxygenase (MMO) and the corresponding reaction mechanism, we prepared a biomimetic photocatalyst with the decoration of Fe 2 O 3 nanoclusters and satellite Fe single atoms immobilized on carbon nitride. The catalyst demonstrates an excellent CH 3 OH productivity of 5.02 mmol ⋅ g cat −1 ⋅ h −1 with CH 3 OH selectivity of 98.5 %. Mechanism studies reveal that the synergy between Fe 2 O 3 nanoclusters and Fe single atoms establishes a dual‐Fe site as MMO for O 2 activation and subsequent CH 4 partial oxidation. Moreover, the light excitation of Fe 2 O 3 nanoclusters with a relative narrow band gap could deliver the electrons and protons to atomic Fe that facilitating the oxygen reduction kinetics for the robust of CH 3 OH synthesis.