Direct Oxidation of Methane to Methanol Enabled by Electronic Atomic Monolayer-Metal Support Interaction

Direct, catalytic oxidation of methane to methanol (MTM) with molecular oxygen is a highly desirable process to valorize methane. We propose that Rh-doped graphene (GR) supported on Ni(111) can be a promising catalyst for MTM with appreciable activity and selectivity. In the absence of the Ni(111) support, a MTM process is difficult. The catalytic activity of the Rh-doped GR is enabled by the Ni(111) support that covalently binds the Rh-doped GR and significantly modifies its properties, leading to facile O-2 activation by the synergy of the Rh dopant and the neighboring carbon atom of GR The highly activated O-2 and the Rh dopant in turn activate CH4. Strikingly, the methane C-H bond breaking is preferred over methanol C-H bond breaking at 473 K. The strong interaction between TM-doped GR and Ni(111) is found to be a general mechanism for regulating the adsorption strength of various molecules, providing important insight for tuning the properties of single-atom catalysts.