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Nature of Ptn/TiO2(110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study

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Department of Chemical Engineering, University of South Carolina, 301 South Main Street, Columbia, South Carolina 29208, United States
Cite this: J. Phys. Chem. C 2011, 115, 39, 19246–19259
Publication Date (Web):August 23, 2011
Copyright © 2011 American Chemical Society
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The electronic structure of small Ptn (n = 1–8) clusters supported on the stoichiometric and partially reduced rutile TiO2(110) surface have been investigated using density functional theory. Pt atoms prefer to form a close-packed structure with (111) facet near an oxygen vacancy of the TiO2 support and a less dense structure with (100) facet away from oxygen vacant sites. The main focus of this study is on identifying a realistic catalyst model for the Pt/TiO2 interface under water-gas shift (WGS) reaction conditions. Constrained ab initio thermodynamic simulations on the stability of oxygen vacancies and formation of adsorbed gas phase molecules such as oxygen, CO, and hydrogen at the metal/oxide interface reveal that under WGS reaction conditions the formation of surface oxygen vacancies are thermodynamically favorable, platinum oxide species (PtOx) can easily be reduced and should not be present, CO adsorbs only weakly on interfacial Pt atoms, and CO poisoning of these sites should be less important. While hydrogen generally interacts weakly with interfacial Pt atoms, it forms very stable hydride species on Pt atoms neighboring an oxygen vacancy of the TiO2(110) support, possibly negatively affecting the WGS reaction rate.

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Effect of vibrational entropies on Gibbs free energies for the adsorption of an oxygen atom and CO molecule on the Pt8/TiO2 surface versus oxygen and CO chemical potentials, respectively. This material is available free of charge via the Internet at

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