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A comparison between metal supported c-ZrO2 and CeO2

Alfredsson, M; Catlow, CRA; (2002) A comparison between metal supported c-ZrO2 and CeO2. PHYS CHEM CHEM PHYS , 4 (24) 6100 - 6108. 10.1039/b204680f.

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Abstract

We present periodic density-functional theory calculations within the GGA Hamiltonian for monolayers of Pd and Pt supported on the {111} surfaces of cubic-ZrO2 and CeO2. We find that the adsorption energies for the Pd-layer on both the zirconia and ceria supports are ca. 200 kJ mol(-1), while the corresponding adsorption energies for the Pt-layers are ca. 400 kJ mol(-1). Our calculations also predict that the Pt Pt interactions are three times stronger (similar to300 kJ mol(-1)) than the corresponding Pd Pd interactions, explaining the different cluster shapes and metal growth modes observed experimentally. Our calculations indicate that the electronic structure of the support determines the geometrical structure of the interface: a tilting of ca. 20 compared to the underlaying ZrO2 substrate is identified, which is not observed for the CeO2 substrate. Furthermore, we propose that the bonding character between the metal ad-layers and the oxide supports is dominated by electrostatic forces, owing to the polarisation of the metal ad-layers; yet a weak hybridisation between the outermost oxygen ions and the metal ad-layers is also present. The CeO2 interfaces investigated show metallic properties as a result of metal induced gap states originating from the metal ad-layers, while the ZrO2 interfaces show a small band gap of ca. 0.1 eV.

Type:Article
Title:A comparison between metal supported c-ZrO2 and CeO2
DOI:10.1039/b204680f
Keywords:ELECTRONIC-STRUCTURE CALCULATIONS, DEFECT CLUSTER FORMATION, OXIDE FUEL-CELL, CUBIC ZIRCONIA, POPULATION ANALYSIS, CERIA, CATALYSTS, SURFACES, PD, SPECTROSCOPY
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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