title: Contributions of electron microscopy to understanding CO adsorption on powder Au/ceria-zirconia catalysts.
abstract: The influence of the highly dispersed gold phase on the CO-support interaction occurring in two 2.5 wt % Au/Ce(0.62)Zr(0.38)O(2) catalysts with medium (Au/CZ-MD) and high (Au/CZ-HD) metal dispersion is quantitatively assessed. For this purpose, we have followed an approach in which high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), computer modelling, volumetric adsorption and FTIR spectroscopy studies are combined. This approach has already been fruitfully applied to the investigation of the specific CO-metal adsorption in Au/ceria-zirconia catalysts. As deduced from the experimental studies reported herein, the presence of gold dramatically increases the amount of CO strongly chemisorbed on the support. Moreover, this amount is sensitive to the metal dispersion, thus suggesting the occurrence of a mechanism in which the CO molecules that are initially adsorbed on the gold nanoparticles are further transferred to the support by means of a spillover process. An annular model is proposed for the growth of the CO phase adsorbed on the ceria-zirconia mixed oxide in the presence of Au. By assuming this model, we have estimated the width of the annulus, Delta r, of the adsorbed CO grown around the Au nanoparticles in Au/CZ-MD and Au/CZ-HD catalysts. This value is found to be very close to Delta r approximately 2 nm in both cases, the coincidence lending some additional support to the model. To further confirm this proposal, we have investigated the influence of CO pre-adsorption on the D(2)-Au/CZ-MD interaction, at 298 K. As revealed by FTIR spectroscopy, the kinetics of the deuterium spillover is significantly disturbed by the pre-adsorbed CO, which is fully consistent with an annular model for the CO adsorption. We conclude from the global analysis of the results reported here and those already available on CO-Au adsorption that the appropriate combination of nanostructural, computer modelling and chemical techniques is a powerful tool allowing us to gain a comprehensive picture of the complex series of processes involved in the CO adsorption on this relevant family of gold catalysts.
authors.affiliation: Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de Cádiz, 11510 Puerto Real, Cadiz, Spain.
authors.forename: José María
authors.initials: JM
authors.lastname: Cíes
authors.forename: Juan José
authors.initials: JJ
authors.lastname: Delgado
authors.forename: Miguel
authors.initials: M
authors.lastname: López-Haro
authors.forename: Ratchaneekorn
authors.initials: R
authors.lastname: Pilasombat
authors.forename: José Antonio
authors.initials: JA
authors.lastname: Pérez-Omil
authors.forename: Susana
authors.initials: S
authors.lastname: Trasobares
authors.forename: Serafin
authors.initials: S
authors.lastname: Bernal
authors.forename: José Juan
authors.initials: JJ
authors.lastname: Calvino