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

Abstract

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 O2 activation by the synergy of the Rh dopant and the neighboring carbon atom of GR. The highly activated O2 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.