Surface sites on Pt–CeO2 mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study

By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt–CeO2 mixed oxide films prepared on CeO2(111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt–CeO2 mixed oxide films caused by annealing in an ultrahigh vacuum. Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO2 film. The peak at 290.5–291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt–CeO2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8–288.0 eV associated with carbonite species formed near Ce3+ cations. The development of surface species on the Pt–CeO2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt4+ or Pt2+. The onset of Pt2+ reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt2+ in Pt–CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt2+ for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt2+ is converted into metallic Pt particles above 300 K.