The adsorption of CO on Pt nanoclusters grown in a regular array on a template provided by the graphene/Ir(111) Moire was investigated by means of infrared-visible sum frequency generation vibronic spectroscopy, scanning tunneling microscopy, X-ray photoelectron spectroscopy from ultrahigh vacuum to near ambient pressure, and ab initio simulations. Both terminally and bridge bonded CO species populate nonequivalent sites of the clusters, spanning from first to second-layer terraces to borders and edges, depending on the particle size and morphology and on the adsorption conditions.
By combining experimental information and the results of the simulations, we observe a significant restructuring of the clusters. Additionally, above room temperature and at 0.1 mbar, Pt clusters catalyze the spillover of CO to the underlying graphene/Ir(111) interface.