Size and structure effects on platinum nanocatalysts: theoretical insights from methanol dehydrogenation.

Methanol dehydrogenation on Pt nanoparticles was studied as a model reaction with the focus on size and structure effects employing the density functional theory approach. The effect of cluster morphology is manifested by the higher adsorption energy of COH x intermediates on vertexes and edges of model nanoparticles compared to closely packed terraces. Moreover, due to the size effect, the adsorption sites of Pt 79 nanoparticles (1.2 nm in diameter) exhibit considerably higher adsorption activity than the same sites of Pt 201 (1.7 nm). Thus, particles with a size of about 1 nm are shown to be more active due to the superposition of two effects: (i) a higher surface fraction of low-coordinated adsorption sites and (ii) higher activity of these sites compared to particles with a size of about 2 nm.