Effects of Charge Transfer on the Adsorption of CO on Small Molybdenum-Doped Platinum Clusters

The interaction of carbon monoxide with platinum alloy nanoparticles is an important problem in the context of fuel cell catalysis. In this work, molybdenum-doped platinum clusters have been studied in the gas phase to obtain a better understanding of the fundamental nature of the Pt–CO interaction in the presence of a dopant atom. For this purpose, Pt_n⁺ and MoPt_n-1⁺ (n=3–7) clusters were studied by combined mass spectrometry and density functional theory calculations, making it possible to investigate the effects of molybdenum doping on the reactivity of platinum clusters with CO. In addition, IR photodissociation spectroscopy was used to measure the stretching frequency of CO molecules adsorbed on Pt_n⁺ and MoPt_n-1⁺ (n=3–14), allowing an investigation of dopant-induced charge redistribution within the clusters. This electronic charge transfer is correlated with the observed changes in reactivity