Beyond reduction cocatalysts: critical role of metal cocatalysts in photocatalytic oxidation of methane with water

Environmentally sustainable and selective conversion of methane to valuable chemicals under ambient conditions is pivotal for the development of next-generation photocatalytic technology. However, due to the lack of microscopic knowledge about non-thermal methane conversion, controlling and modulating photocatalytic oxidation processes driven by photogenerated holes remain a challenge. Here, we report novel function of metal cocatalysts to accept photogenerated holes and dominate the oxidation selectivity of methane, which is clearly beyond the conventional concept in photocatalysis that the metal cocatalysts loaded on the surfaces of semiconductor photocatalysts mostly capture photogenerated electrons and dominate reduction reactions exclusively. The novel photocatalytic role of metal cocatalysts was verified by operando molecular spectroscopy combined with real-time mass spectrometry for metal-loaded Ga2O3 model photocatalysts under methane gas and water vapor at ambient temperature and pressure. Our concept of metal cocatalysts that work as active sites for both photocatalytic oxidation and reduction provides a new understanding of photocatalysis and a solid basis for controlling the non-thermal redox reactions by metal-cocatalyst engineering.