Understanding the Curvature Effect on the Structure and Bonding of MoCy Nanoparticles on Carbon Supports

The interaction between molybdenum carbide (MoCy) nanoparticles and both flat and curved graphene surfaces, serving as models for carbon nanotubes, was investigated by means of density functional theory. A variety of MoCy nanoparticles with different sizes and stoichiometries have been used to explore different adsorption sites and modes across models with different curvature degrees. On flat graphene, off-stoichiometric MoCy featuring more low-coordinated Mo atoms exhibits stronger interaction and increased electron transfers from the carbide to the carbon substrate. This preferentially occurs through support C and Mo atoms leading to the formation of additional Mo–C bonds. Notably, the MoCy adsorption strength increases on concave surfaces and decreases on convex surfaces, showing a strong linear correlation with the surface curvature. This curvature-dependent behavior alters the charge state of the nanoparticles, making them more/less positively charged in concave/convex regions. The present results demonstrate that the interaction strength can be effectively tuned by manipulating the carbide stoichiometry, the substrate curvature, and the local concave/convex environments, providing valuable guidelines for the rational design of MoCy/C-based catalysts.