How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry

Authors

  • Dr. Marc Armbrüster,

    1. Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str. 40, 01187 Dresden (Germany)
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  • Dr. Malte Behrens,

    Corresponding author
    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
    • Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Dr. Fabrizio Cinquini,

    1. Université de Lyon, CNRS, Institut de Chimie de Lyon, Ecole Normale Supérieure de Lyon, 46 allée d1Italie, F-69364 Lyon Cedex 07 (France)
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  • Dr. Karin Föttinger,

    1. Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01, 1060 Vienna (Austria)
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  • Prof. Dr. Yuri Grin,

    1. Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str. 40, 01187 Dresden (Germany)
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  • Dr. Andreas Haghofer,

    1. Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01, 1060 Vienna (Austria)
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  • Prof. Dr. Bernhard Klötzer,

    1. Institute of Physical Chemistry, University of Innsbruck, Innrain 52 A, A-6020 Innsbruck (Austria)
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  • Dr. Axel Knop-Gericke,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Harald Lorenz,

    1. Institute of Physical Chemistry, University of Innsbruck, Innrain 52 A, A-6020 Innsbruck (Austria)
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  • Antje Ota,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Dr. Simon Penner,

    1. Institute of Physical Chemistry, University of Innsbruck, Innrain 52 A, A-6020 Innsbruck (Austria)
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  • Jan Prinz,

    1. nanotech@surfaces, Empa - Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600 Duebendorf (Switzerland)
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  • Dr. Christoph Rameshan,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
    2. Institute of Physical Chemistry, University of Innsbruck, Innrain 52 A, A-6020 Innsbruck (Austria)
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  • Dr. Zsolt Révay,

    1. Nuclear Analysis and Radiography Department, Centre for Energy Research, Hungarian Academy of Sciences, P.O. Box 49, 1525 Budapest 114 (Hungary)
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  • Dr. Dirk Rosenthal,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Prof. Dr. Günther Rupprechter,

    1. Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01, 1060 Vienna (Austria)
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  • Prof. Dr. Philippe Sautet,

    1. Université de Lyon, CNRS, Institut de Chimie de Lyon, Ecole Normale Supérieure de Lyon, 46 allée d1Italie, F-69364 Lyon Cedex 07 (France)
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  • Prof. Dr. Robert Schlögl,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Dr. Lidong Shao,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Dr. László Szentmiklósi,

    1. Nuclear Analysis and Radiography Department, Centre for Energy Research, Hungarian Academy of Sciences, P.O. Box 49, 1525 Budapest 114 (Hungary)
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  • Dr. Detre Teschner,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Dr. Daniel Torres,

    1. Université de Lyon, CNRS, Institut de Chimie de Lyon, Ecole Normale Supérieure de Lyon, 46 allée d1Italie, F-69364 Lyon Cedex 07 (France)
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  • Dr. Ronald Wagner,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Roland Widmer,

    1. nanotech@surfaces, Empa - Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600 Duebendorf (Switzerland)
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  • Gregor Wowsnick

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck.Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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Abstract

Discussed are the recent experimental and theoretical results on palladium-based catalysts for selective hydrogenation of alkynes obtained by a number of collaborating groups in a joint multi-method and multi-material approach. The critical modification of catalytically active Pd surfaces by incorporation of foreign species X into the sub-surface of Pd metal was observed by in situ spectroscopy for X=H, C under hydrogenation conditions. Under certain conditions (low H2 partial pressure) alkyne fragmentation leads to formation of a Pd[BOND]C surface phase in the reactant gas feed. The insertion of C as a modifier species in the sub-surface increases considerably the selectivity of alkyne semi-hydrogenation over Pd-based catalysts through the decoupling of bulk hydrogen from the outmost active surface layer. DFT calculations confirm that Pd[BOND]C hinders the diffusion of hydridic hydrogen. Its formation is dependent on the chemical potential of carbon (reactant partial pressure) and is suppressed when the hydrogen/alkyne pressure ratio is high, which leads to rather unselective hydrogenation over in situ formed bulk Pd[BOND]H. The beneficial effect of the modifier species X on the selectivity, however, is also present in intermetallic compounds with X=Ga. As a great advantage, such PdxGay catalysts show extended stability under in situ conditions. Metallurgical, clean samples were used to determine the intrinsic catalytic properties of PdGa and Pd3Ga7. For high performance catalysts, supported nanostructured intermetallic compounds are more preferable and partial reduction of Ga2O3, upon heating of Pd/Ga2O3 in hydrogen, was shown to lead to formation of Pd[BOND]Ga intermetallic compounds at moderate temperatures. In this way, Pd5Ga2 and Pd2Ga are accessible in the form of supported nanoparticles, in thin film models, and realistic powder samples, respectively.

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