Transport Mediating Core-Shell Photocatalyst Architecture for Selective Alkane Oxidation

The high activation barrier of the C-H bond in methane, combined with the high propensity of methanol and other liquid oxygenates toward overoxidation to CO₂, have historically posed significant scientific and industrial challenges to the selective and direct conversion of methane to energy-dense fuels and chemical feedstocks. Here, we report a unique core-shell nanostructured photocatalyst, silica encapsulated TiO₂ decorated with AuPd nanoparticles (TiO₂@SiO₂-AuPd), that prevents methanol overoxidation on its surface and possesses high selectivity and yield of oxygenates even at high UV intensity. This room-temperature approach achieves high selectivity for oxygenates (94.5%) with a total oxygenate yield of 15.4 mmol/g_cat·h at 9.65 bar total pressure of CH₄ and O₂. The working principles of this core-shell photocatalyst were also systematically investigated. This design concept was further demonstrated to be generalizable for the selective oxidation of other alkanes.