Direct functionalization of methane into ethanol over copper modified polymeric carbon nitride via photocatalysis

Direct valorization of methane to its alcohol derivative remains a great challenge. Photocatalysis arises as a promising green strategy which could exploit hydroxyl radical (center dot OH) to accomplish methane activation. However, both the excessive center dot OH from direct H2O oxidation and the neglect of methane activation on the material would cause deep mineralization. Here we introduce Cu species into polymeric carbon nitride (PCN), accomplishing photocatalytic anaerobic methane conversion for the first time with an ethanol productivity of 106 mu mol g(cat)(-1) h(-1). Cu modified PCN could manage generation and in situ decomposition of H2O2 to produce center dot OH, of which Cu species are also active sites for methane adsorption and activation. These features avoid excess center dot OH for overoxidation and facilitate methane conversion. Moreover, a hypothetic mechanism through a methane-methanol-ethanol pathway is proposed, emphasizing the synergy of Cu species and the adjacent C atom in PCN for obtaining C-2 product.