Light-Induced Dynamic Restructuring of Cu Active Sites on TiO₂ for Low-Temperature H₂ Production from Methanol and...

The structure and configuration of reaction centers, which dominantly govern the catalytic behaviors, often undergo dynamic transformations under reaction conditions, yet little is known about how to exploit these features to favor the catalytic functions. Here, we demonstrate a facile light activation strategy over a TiO₂-supported Cu catalyst to regulate the dynamic restructuring of Cu active sites during low-temperature methanol steam reforming. Under illumination, the thermally deactivated Cu/TiO₂ undergoes structural restoration from inoperative Cu₂O to the originally active metallic Cu caused by photoexcited charge carriers from TiO₂, thereby leading to substantially enhanced activity and stability. Given the low-intensity solar irradiation, the optimized Cu/TiO₂ displays a H₂ production rate of 1724.1 μmol g^-1 min^-1, outperforming most of the conventional photocatalytic and thermocatalytic processes. Taking advantages of the strong light-matter-reactant interaction, we achieve in situ manipulation of the Cu active sites, suggesting the feasibility for real-time functionalization of catalysts.