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Oxidation of magnesia-supported Pd-clusters leads to the ultimate limit of epitaxy with a catalytic function

Nature Materials volume 5, pages 44–47 (2006)Cite this article

Abstract

Oxide-supported transition-metal clusters and nanoparticles have attracted significant attention owing to their important role as components of model catalysts1,2,3,4,5,6, sensors7, solar cells8 and magnetic recording devices9. For small clusters, functionality and structure are closely interrelated. However, knowledge of the structure of the bare cluster is insufficient as the interaction with the chemical environment might cause drastic structural changes. Here we show by ab initio simulations based on the density functional theory that the reaction with molecular oxygen transforms small, non-crystalline, magnesia-supported Pd-clusters to crystalline PdxOy nano-oxide clusters that are in epitaxy with the underlying support. Restructuring of the Pd backbone is controlled by the electrostatic interaction with magnesia leading to a strong reduction of the O2 dissociation barrier. The supported PdxOy clusters are likely to serve as Mars–van Krevelen10 oxygen reservoirs in catalytic oxidation reactions as observed for PdO overlayers11 and demonstrated here for the oxidation of CO molecules.

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Figure 1: The oxidation of magnesia-supported and gas-phase Pd4.
Figure 2: Structural growth motif of bare and oxidized palladium clusters on MgO(FC).
Figure 3: Possible CO oxidation reaction pathways A–B–C–D–E, A–F–G–H–E and A–I–J–K–E on O4Pd9/MgO(FC).

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Acknowledgements

We thank U. Heiz for the communication of unpublished results and fruitful discussions. This work was supported by the Deutsche Forschungsgemeinschaft within SPP 1153, the Fraunhofer MAVO for Multiscale Materials Modelling (MMM) and the Academy of Finland (AF). M.M. and H.H. acknowledge the DAAD-AF bilateral travel grant for the project ‘Supported Metal Clusters and Nanoparticles: Electronic Structure, Optical Properties and Nanocatalysis’. Computations were performed at NIC in Jülich, Germany, and at the CSC—the Finnish IT Center for Science in Espoo, Finland.

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Authors and Affiliations

  1. Freiburg Materials Research Center, University of Freiburg, D-79104, Freiburg, Germany

    Bernd Huber & Michael Moseler

  2. Fraunhofer Institute for Mechanics of Materials, Wöhlerstrasse 11, D-79108, Freiburg, Germany

    Bernd Huber, Pekka Koskinen & Michael Moseler

  3. Department of Physics, NanoScience Center, FIN-40014 University of Jyväskylä, Finland

    Hannu Häkkinen

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  1. Bernd Huber
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Correspondence to Michael Moseler.

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Huber, B., Koskinen, P., Häkkinen, H. et al. Oxidation of magnesia-supported Pd-clusters leads to the ultimate limit of epitaxy with a catalytic function. Nature Mater 5, 44–47 (2006). https://doi.org/10.1038/nmat1533

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