Abstract Methane conversion to higher hydrocarbons requires harsh reaction conditions due to high energy barriers associated with C−H bond activation. Herein, we report a systematic investigation of photocatalytic oxidative coupling of methane (OCM) over transition‐metal‐loaded ZnO photocatalysts. A 1 wt % Au/ZnO delivered a remarkable C2‐C4 hydrocarbon production rate of 683 μmol g−1 h−1 (83 % C2‐C4 selectivity) under light irradiation with excellent photostability over two days. The metal type and its interaction with ZnO strongly influence the selectivity toward C−C coupling products. Photogenerated Zn+‐O− sites enable CH4 activation to methyl intermediates (*CH3) migrating onto adjacent metal nanoparticles. The nature of the *CH3‐metal interaction controls the OCM products. In the case of Au, strong d‐σ orbital hybridization reduces metal‐C−H bond angles and steric hindrance, thereby enabling efficient methyl coupling. Findings indicate the d‐σ center may be a suitable descriptor for predicting product selectivity during OCM over metal/ZnO photocatalysts.
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