Shape-dependent CO chemisorption on Pt₁₃ nanocluster deposited on reduced TiO₂(110)

This article delves into the impact of nanoparticle shape on CO chemisorption and the reactivity of Pt₁₃ nanocatalysts supported on reduced TiO₂(110). Distinct reactivity in carbon monoxide adsorption is observed among nanoparticles, all composed of 13 platinum atoms but varying in shape. The calculated formation and CO adsorption energies are correlated to the electronic properties of the system and the oxidation states of the Pt atoms involved. Through an analysis of band shifting during the deposition of Pt clusters onto the oxide, and a comparison of the valence band maximum with the measured oxidation potential for the CO to CO₂ reaction, we make predictions about the system's oxidation capability in this reaction. Our findings suggest that Pt₁₃ clusters with cuboid, double triangle DT2 and octahedral Oh shapes, supported on the surface, are particularly advantageous for catalyzing the conversion of CO to CO₂. Within these geometries, several configurations for CO adsorption are evaluated, focusing on the ratio between anionic and cationic Pt sites. This ratio appears to govern the activity for CO oxidation, aligning with recent experimental reports.