CO-Free Hydrogen Production for Fuel Cell Applications over Au/CeO2 Catalysts: FTIR Insight into the Role of Dopant

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Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria, and Department of Inorganic, Physical and Materials Chemistry and NIS Centre of Excellence, University of Turin, via P. Giuria 7, 10125 Turin, Italy
†Part of the special issue “Green Chemistry in Energy Production Symposium”.
* Corresponding author. Tel: (+359 2) 979 2528. Fax: (+359 2) 971 2967. E-mail: [email protected]
‡Bulgarian Academy of Sciences.
§University of Turin.
Cite this: J. Phys. Chem. A 2010, 114, 11, 3909–3915
Publication Date (Web):September 29, 2009
Copyright © 2009 American Chemical Society
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The impact of ceria doping by Zn (atomic ratio Zn/(Zn + Ce) = 0.05) on the structural and catalytic properties of Au/CeO2 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 (H2, D2), and after admission of CO and its subsequent interaction with 18O2 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/CeO2 sample than on the Au/Zn−CeO2 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.

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