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Catalytic Activity and Surface Characterization Study of Pd Supported on Nanocrystalline and Polycrystalline CeO2

Published online by Cambridge University Press:  21 February 2011

Gar B. Hoflund ,
Zhenhua Li ,
Timothy J. Campbell ,
William S. Epling  and
Horst W. Hahn
Gar B. Hoflund
Affiliation:
Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611, USA
Zhenhua Li
Affiliation:
Department of Chemical Engineering, Tianjin University, Tianjin 300072, PRC
Timothy J. Campbell
Affiliation:
AFRL/MLQ, 139 Barnes Drive, Tyndall AFB, L 32403-5323, USA
William S. Epling
Affiliation:
Department of Chemical Engineering, Box 870203, The University of Alabama, Tuscaloosa, L 35487, USA
Horst W. Hahn
Affiliation:
Darmstadt University of Technology, FB 21-Materials Science Department, Thin Films Division, etersenstrasse 23, 4287 Darmstadt, Germany
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Abstract

The catalytic activity of polycrystalline and nanocrystalline CeO2-supported Pd (Pd/pCeO2 and Pd/nCeO2) has been determined as a function of temperature and Pd loading. While the untreated nCeO2 support gives 50% methane conversion at 420°C, the untreated pCeO2 support exhibits little activity under the conditions examined due to its low surface area. A Pd loading of 5 wt% increases the activity of pCeO2 to 50% conversion at 260°C, while a 40 wt% Pd loading on nCeO2 exhibits a relatively smaller activity increase, yielding 50% conversion at 240°C. On a mass basis the 40 wt% Pd/nCeO2 catalyst is the most active tested in this study, but it is less active than the 5 wt% Pd/pCeO2 catalyst on a surface-area basis. Furthermore, the activity of the 40 wt% Pd/nCeO2 catalyst does not decrease during 100 hrs of exposure to CH4 and O2 at 250°C.

X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) have been used to characterize the surfaces of both bare supports and Pd-containing catalysts before and after exposure to reactor conditions. The XPS results reveal that the Pd surface concentration is more than an order of magnitude higher for 5 wt% Pd/pCeO2 than for 5 wt% Pd/nCeO2 due to the larger surface area of nCeO2 and that the 40 wt% Pd/nCeO2 catalyst has a lower Pd loading on a surface-area basis than the 5 wt% Pd/pCeO2 catalyst. Most of the supported Pd is in the form of PdO, but higher PdO2/PdO ratios are observed for both CeO2 supports compared to Pd supported on ZrO2 or CO3O4. Furthermore, a significant amount of metallic Pd forms on Pd/nCeO2 but not on Pd/pCeO2 during reaction. The nanocrystalline and polycrystalline CeO2 behave differently chemically which is consistent with the fact that the nanocrystalline catalysts are less active on a surface-area basis. Accumulation of H20 on the Pd/pCeO2 surface during reaction is significant but not on the Pd/nCeO2 surface. This suggests that the rate limiting step may be H2O desorption on Pd/pCeO2 while for Pd on nCeO2 adsorption of methane appears to be the slow step. The ISS data indicate that the outermost atomic layer of Pd/nCeO2 consists mostly of O and C, which is not the case for Pd/pCeO2. Site blockage by these species may also contribute to the lower activity on a surface-area basis of Pd/nCeO2 compared to Pd/pCeO2.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 581: Symposium F – Nanophase & Nanocomposite Materials II , 1999 , 449
Copyright
Copyright © Materials Research Society 2000

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References

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