Molecular mechanisms of methane dry reforming on Co3Mo3N catalyst with dual sites

Abstract

The catalytic performance of Co₃Mo₃N for dry reforming of methane (DRM) was investigated using periodic density functional theory (DFT). The full mechanism revealed that Co₃Mo₃N(111) activates both CH₄ and CO₂ at different catalytic regimes, which also facilitates CO production to proceed via COH and CHO intermediates. Aided by linear scaling relationships, steady-state microkinetic modeling confirms promising DRM reactivity, thanks to the unique dual-site configuration on monolithic Co₃Mo₃N(111) when compared to monofunctional transition metals. Efficient for C–H bond activation, Co₃Mo₃N(111) is also effective at residual carbon removal due to facile CO₂ dissociation, and thus, tolerates surface C species. In synergy, the presence of moderate C and CH coverages helps control surface O species. This work provides insights into catalyst systems that contain two beneficial functionalities for effective and durable DRM operations.