Enhanced Photocatalytic Oxidative Coupling of Methane over Metal-Loaded TiO₂ Nanowires

The photocatalytic oxidative coupling of methane (OCM) on metal-loaded one-dimensional TiO₂ nanowires (TiO₂ NWs) was performed. With metal loading, the electric and optical properties of TiO₂ NWs were adjusted, contributing to the improvement of the activity and selectivity of the OCM reaction. In the photocatalytic OCM reaction, the 1.0 Au/TiO₂ NW catalyst exhibits an outstanding C₂H₆ production rate (4901 μmol g^-1 h^-1) and selectivity (70%), alongside the minor production of C₃H₈ and C₂H₄, achieving a total C₂-C₃ hydrocarbon selectivity of 75%. In contrast, catalysts loaded with Ag, Pd, and Pt show significantly lower activity, with Pt/TiO₂ NWs producing only CO₂, indicating a propensity for the deep oxidation of methane. The O₂-TPD analyses reveal that Au facilitates mild O₂ adsorption and activation, whereas Pt triggers excessive oxidation. Spectroscopic and kinetic studies demonstrate that Au loading not only enhances the separation efficiency of photogenerated electron-hole pairs, but also promotes the generation of active oxygen species in moderate amounts, which facilitates the formation of methyl radicals and their coupling into C₂H₆ while suppressing over-oxidation to CO₂. This work provides novel insights and design strategies for developing efficient photocatalysts.