Preference for low-coordination sites by adsorbed CO on small platinum nanoparticles

FTIR spectra of ¹²CO adsorbed on poly(vinylpyrrolidone) (PVP)-stabilized colloidal platinum at room temperature were acquired and studied. Two new bands, at 2021 cm^-1 and 1994 cm^-1, were observed for the first time and were assigned to the stretching vibrations of CO linearly adsorbed on the Pt surface at edge and corner sites, respectively. The relative intensities of these two bands were found to vary with the coverage of CO, where the smallest particles showed the highest intensity, corresponding to the relative quantities of edge and corner sites per unit surface. The vibrational spectra signals reported for terrace sites on colloidal Pt red-shifted as the particle size was decreased, which showed the electronic interactions between the Pt surface and PVP, with PVP acting as an electron donor.