Supported Molybdenum Carbide Nanoparticles as Hot Hydrogen Reservoirs for Catalytic Applications

Transition metal carbides have been long proposed as replacements for expensive Pt-group transition metals as heterogeneous catalysts for hydrogenation reactions, featuring similar or superior activities and selectivities. Combining experimental observations and theoretical calculations, we show that the hydrogenating capabilities of molybdenum carbide can be further improved by nanostructuring, as seen on MoCy nanoclusters anchored on an inert Au(111) support, revealing a more prominent role of Mo active sites in the easier H-2 adsorption, dissociation, H adatom diffusion, and elongated chemisorbed H-2 Kubas moieties formation when compared to the bulk delta-MoC(001) surface, thus explaining the observed stronger H-2 interaction and the larger formation of CHx species, making these systems ideal to catalyze hydrogenation reactions.