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Self-assembled Pt nanostructures, which are formed by evaporation and subsequent diffusion limited aggregation of Pt on graphite, have been studied by photoemission and scanning electron microscopy. Adsorption of CO has been studied by temperature programmed desorption. Charge induced Pt 4f core level shifts in the order of 1 eV that depend on the effective dimensions of the nanostructures have been observed, and effective dimensions of the Pt structures have been defined based on the Pt 4f core level shifts. The effective dimensions of the Pt structures have been correlated with changes in the thermal desorption of adsorbed CO. It is observed that smaller effective dimensions in the few nanometer range result in lower desorption temperatures of up to 50 K. The possible role of hot electrons in the adsorption process has been discussed.