A Metastable State Facilitates Low Temperature CO Oxidation over Pt Nanoparticles

The dynamic response of heterogeneous catalytic materials to their environment opens a wide variety of possible surface states which may have increased catalytic activity. In this work, we find that it is possible to generate a surface state with increased catalytic activity over metallic 2 nm Pt nanoparticles by performing a thermal treatment of the CO*-covered Pt catalyst. This state is characterised by its ability to oxidise CO to CO₂ at room temperature. By combining pressure pulse experiments with in situ spectroscopy we correlate the formation of this high-activity state with the desorption of weakly bound CO* molecules from well-coordinated Pt sites. This high-activity state is metastable, degrading after elevated thermal treatments or upon readsorption of CO at room temperature. We conclude that this metastable state is highly localised to the surface of the nanoparticle, however its exact atomic structure remains open to speculation.