Selective Photocatalytic Oxidative Coupling of Methane via Regulating Methyl Intermediates over Metal/ZnO Nanoparticles.

Wang, Pu; Shi, Run; Zhao, Yunxuan; Li, Zhenhua; Zhao, Jiaqing; Zhao, Jiaqi; Waterhouse, Geoffrey I. N.; Wu, Li‐Zhu; Zhang, Tierui

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.

OXIDATIVE coupling; ORBITAL hybridization; ZINC oxide; METAL nanoparticles; COUPLING reactions (Chemistry); STEAM reforming

Angewandte Chemie, 2023, Vol 135, Issue 23, p1

0044-8249

Academic Journal

10.1002/ange.202304301