AuPd Nanoalloy-Decorated TS-1 Zeolite Photocatalyst for Highly Selective Methane-to-Methanol Oxidation at Low Temperature

High Resolution Image Download MS PowerPoint Slide The direct oxidation of methane to methanol at room temperature is a highly sought-after but challenging reaction due to methane’s inert C−H bond and methanol overoxidation. Conventional approaches often require high temperature and pressure or special oxidants. Here, we report an Au x Pd y /TS-1 composite photocatalyst with tunable Au/Pd ratios that achieves highly selective methane-to-methanol conversion at near-room temperature using water as the oxidant. An optimized Au 0.1 Pd 0.05 /TS-1 photocatalyst exhibits an activity of 64.7 mmol g AuPd −1 h −1 and a turnover frequency of 19.1 h -1 with 100% methanol selectivity under simulated solar light. This performance arises from the efficient electron-hole generation by encapsulated nanoalloy AuPd clusters, generating ·OH and ·CH 3 radicals for methane activation and water oxidation, as evidenced by in situ EPR and DRIFT spectroscopy. DFT calculations show that Au sites preferentially mediate the formation of methanol via surface-bound *CH 3 and *OH intermediates. Alloy-induced Pd→Au charge redistribution modulates CH 4 /H 2 O activation energetics and weakens methanol binding. This study demonstrates an efficient and mild route for highly selective methane utilization under mild conditions.