CO-free hydrogen production for fuel cell applications over Au/CeO2 catalysts: FTIR insight into the role of dopant.

The impact of ceria doping by Zn (atomic ratio Zn/(Zn + Ce) = 0.05) on the structural and catalytic properties of Au/CeO(2) catalyst was studied. The ceria modification influenced the catalytic activity toward purification of hydrogen via water-gas shift (WGS) and preferential CO oxidation (PROX) reactions in a different way: it diminished the WGS activity and improved the PROX performance. A characterization by FTIR spectroscopy was conducted to explain differences in the catalytic performance. The nature of gold active species after different pretreatments, under different atmospheres (H(2), D(2)), and after admission of CO and its subsequent interaction with (18)O(2) was investigated. Evidence has been found of the dissociation of hydrogen at room temperature on gold, producing on the oxidized sample a broad absorption assigned to Au-OH vibrations, whereas on the reduced one, bands at 3200 and 1800 cm(-1) ascribed, respectively, to Au-OH and Au-H species have been detected. For the first time, the formation of Au-hydride on supported heterogeneous catalysts was proposed. These features were stronger on the Au/CeO(2) sample than on the Au/Zn-CeO(2) sample. The availability of highly dispersed gold clusters in contact with oxygen vacancies on the ceria surface could contribute to higher WGS activity, whereas the steps of small gold particles are the active sites for both CO and oxygen activation during the PROX reaction.

CO adsorption on gold clusters stabilized on ceria-titania mixed oxides: comparison with reference catalysts.

Fourier transform infrared spectra of CO adsorption from 120 K up to room temperature on two gold catalysts supported on different mixed ceria-titania oxides are discussed in comparison with those obtained on Au/TiO(2) and Au/Fe(2)O(3) reference catalysts provided by the World Gold Council. The spectra of adsorbed CO, run on the different samples before preliminary treatment, are shown and compared with those of the untreated catalysts and of the samples reduced either in CO or in hydrogen. Big differences have been found between the ceria-titania supported samples and the reference ones: unusual absorption bands, irreversible to outgassing, have been detected after CO interaction on the untreated and oxidized ceria containing samples. These absorptions are assigned to CO on Au(n)(+) small clusters stabilized at the ceria defects. By reduction in hydrogen, negatively charged Au(n)(-) species are produced on the same sample. Oxidized small particles are present on the reference catalysts, but only on the untreated samples; after treatment, only metallic step sites are evident.