The conversion of CO2 to methanol on orthorhombic β-Mo2C and Cu/β-Mo2C catalysts: mechanism for admetal induced change in the selectivity and activity

The conversion of CO2 into methanol catalyzed by β-Mo2C and Cu/β-Mo2C surfaces has been investigated by means of a combined experimental and theoretical study. Experiments have shown the direct activation and dissociation of the CO2 molecule on bare β-Mo2C, whereas on Cu/β-Mo2C, CO2 must be assisted by hydrogen for its conversion. Methane and CO are the main products on the clean surface and methanol production is lower. However, the deposition of Cu clusters avoids methane formation and increases methanol production even above that corresponding to a model of the technical catalyst. DFT calculations on surface models of both possible C- and Mo-terminations, corroborate the experimental observations. Calculations for the clean Mo-terminated surface reveal the existence of two possible routes for methane production (C + 4H → CH4; CH3O + 3H → CH4 + H2O) which are competitive with methanol synthesis, displaying slightly lower energy barriers. On the other hand, a model for Cu deposited clusters on the Mo- terminated surface points towards a new route for methanol and CO production avoiding methane formation. The new route is a direct consequence of the generation of a Mo2C-Cu interface. The present experimental and theoretical results entail the interesting catalytic properties of Mo2C as an active support of metallic nanoparticles, and also illustrate how the deposition of a metal can drastically change the activity and selectivity of a carbide substrate for CO2 hydrogenation