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Rutile-Deposited Pt–Pd clusters: A Hypothesis Regarding the Stability at 50/50 Ratio

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Department of Chemistry and Biochemistry, University of California, 607 Charles E Young Drive East, Box 951569, Los Angeles, California 90095, United States
California NanoSystems Institute, 570 Westwood Plaza, Los Angeles, California 90095, United States
Cite this: ACS Catal. 2014, 4, 10, 3570–3580
Publication Date (Web):September 4, 2014
https://doi.org/10.1021/cs5011426
Copyright © 2014 American Chemical Society

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    Abstract

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    Mixed Pt–Pd clusters deposited on oxides have been of great interest to catalysis. Clusters containing Pt and Pd in roughly equal proportions were found to be unusually stable against sintering, one of the major mechanisms of catalyst deactivation. After aging of such catalysts, the 50/50 Pt–Pd and Pd–O clusters appeared to be the two most prevalent phases. The reason for the enhanced stability of these equally proportioned clusters has remained unclear. In the following, sintering of mixed Pt–Pd clusters on TiO2(110) for various initial atomic concentrations of Pt and Pd and at a range of catalytically relevant temperatures was simulated. It is confirmed that equally mixed clusters have the relatively highest survival rate. Surprisingly, subnanoclusters containing Pt and Pd in all proportions have very similar geometries and chemical bonding, revealing no apparent explanation for favoring the 1:1 Pt/Pd ratio. However, it was discovered that at high temperatures, the 50/50 clusters have considerably more thermally accessible isomers than clusters containing Pt and Pd in other proportions. Hence, one of the reasons for stability is entropic stabilization. Electrostatics also plays a key role as a subtle charge redistribution, and a shift of electron density to the slightly more electronegative Pt results in the partially charged atoms being further stabilized by intracluster Coulomb attraction; this effect is greatest for 1:1 mixtures.

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    Ab initio calculation of Pt–Pd clusters. Dimers and trimers of mixed Pt–Pd clusters.This material is available free of charge via the Internet at http://pubs.acs.org.

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