Stability of Platinum Nanoparticles Supported on SiO2/Si(111): A High-Pressure X-ray Photoelectron Spectroscopy Study

The stability of Pt nanoparticles (NPs) supported on ultrathin SiO2 films on Si(111) was investigated in situ under H-2 and O-2 (0.5 Torr) by high-pressure X-ray photoelectron spectroscopy (HP-XPS) and ex situ by atomic force microscopy (AFM). No indication of sintering was observed up to 600 degrees C in both reducing and oxidizing environments for size-selected Pt NPs synthesized by inverse micelle encapsulation. However, HP-XPS revealed a competing effect of volatile PtOx desorption from the Pt NPs (similar to 2 and similar to 4 nm NP sizes) at temperatures above 450 degrees C in the presence of 0.5 Tort of O-2. Under oxidizing conditions, the entire NPs were oxidized, although with no indication of a PtO2 phase, with XPS binding energies better matching PtO. The stability of catalytic NPs in hydrogenation and oxidation reactions is of great importance due to the strong structure sensitivity observed in a number of catalytic processes of industrial relevance. An optimum must be found between the maximization of the surface active sites and metal loading (i.e., minimization of the NP size), combined with the maximization of their stability, which, as it will be shown here, is strongly dependent on the reaction environment.