Stability and chemisorption properties of ultrathin TiOx/Pt(111) films and Au/TiOx/Pt(111) model catalysts in reactive atmospheresElectronic supplementary information (ESI) available: Fig. S1 and S2: Representative Au 4f XPS data of the Au(0.9 MLeq)/TiOx/Pt(111) model catalysts before and after pure CO and CO–O2(1 : 1) HP exposures at 100 mbar. Fig. S3: Representative STM image taken on Au(0.9 MLeq)/w′-TiOx/Pt(111) exposed to 100 mbar of a CO–O2(1 : 1) mixture. See DOI: 10.1039/c000884b

The stability of three ultrathin TiOx/Pt(111) films with different stoichiometry and defectivity and the corresponding Au/TiOx/Pt(111) model catalysts in CO or a CO–O2(1 : 1) gas mixture up to a pressure of 100 mbar has been investigated. According to previous studies, the ultrathin films proved to be effective substrates to deposit in UHV Au nanoparticles with specific morphologies and lateral sizes ranging between 1 and 6 nm. The films have been characterized before and after the exposure using X-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED) and scanning tunnelling microscopy (STM). Additional in situmeasurements of the CO chemisorption behavior were performed using polarization-modulation infrared reflection–absorption spectroscopy (PM-IRAS). A fully oxidized film is stable in CO and CO–O2(1 : 1) ambient, while the reduced films undergo an oxidative dewetting process at RT in the latter atmosphere. This process ultimately produces a nano-composite surface, where very tiny (from 0.5 to 3 nm lateral sizes) titania nanograins are mixed with open, uncovered areas of the Pt substrate. IRAS measurements on the corresponding Au/TiOx/Pt(111) model catalysts demonstrated that the CO chemisorption strongly depends on the Au nanoparticle size and morphology, while the actual Ti oxidation state of the oxide support does not seem to play a significant role. [ABSTRACT FROM AUTHOR]