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.