Selective Catalytic Oxidation of Methane to Methanol in Aqueous Medium over Copper Cations Promoted by Atomically Dispersed Rhodium on TiO₂

Direct conversion of methane into value‐added chemicals, such as methanol under mild conditions, is a promising route for industrial applications. In this work, atomically dispersed Rh on TiO 2 suspended in an aqueous solution was used for the oxidation of methane to methanol. Promoted by copper cations (as co‐catalyst) in solution, the catalysts exhibited high activity and selectivity for the production of methanol using molecular oxygen with the presence of carbon monoxide at 150 °C with a reaction pressure of 31 bar. Millimole level yields of methanol were reached with the selectivity higher than 99 % using the Rh/TiO 2 catalysts with the promotion of the copper cation. CO was the reductive agent to generate H 2 from H 2 O, which led to the formation of H 2 O 2 through the reaction of H 2 and O 2 . Atomically dispersed Rh activated the C−H bond in CH 4 and catalyzed the oxidation using H 2 O 2 . Copper cations maintained the low‐valence state of Rh. Moreover, copper acted as a scavenger for suppressing the overoxidation, thus leading to the high selectivity of methanol.