How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions

The Role of Subsurface Chemistry

Marc Armbrüster, Malte Behrens, Fabrizio Cinquini, Karin Föttinger, Yuri Grin, Andreas Haghofer, Bernhard Klötzer, Axel Knop-Gericke, Harald Lorenz, Antje Ota, Simon Penner, Jan Prinz, Christoph Rameshan, Zsolt Révay, Dirk Rosenthal, Günther Rupprechter, Philippe Sautet, Robert Schlögl, Lidong Shao, L. Szentmiklósi & 5 others Detre Teschner, Daniel Torres, Ronald Wagner, Roland Widmer, Gregor Wowsnick

Research output: Contribution to journalArticle

133 Citations (Scopus)

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 insitu spectroscopy for X=H, C under hydrogenation conditions. Under certain conditions (low H 2 partial pressure) alkyne fragmentation leads to formation of a Pd, 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-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 insitu formed bulk Pd-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 Pd xGa y catalysts show extended stability under insitu conditions. Metallurgical, clean samples were used to determine the intrinsic catalytic properties of PdGa and Pd 3Ga 7. For high performance catalysts, supported nanostructured intermetallic compounds are more preferable and partial reduction of Ga 2O 3, upon heating of Pd/Ga 2O 3 in hydrogen, was shown to lead to formation of Pd-Ga intermetallic compounds at moderate temperatures. In this way, Pd 5Ga 2 and Pd 2Ga are accessible in the form of supported nanoparticles, in thin film models, and realistic powder samples, respectively.

Original languageEnglish
Pages (from-to)1048-1063
Number of pages16
JournalChemCatChem
Volume4
Issue number8
DOIs
Publication statusPublished - Aug 2012

Fingerprint

Catalyst selectivity
Palladium
alkynes
Alkynes
Hydrogenation
hydrogenation
palladium
selectivity
chemistry
Hydrogen
intermetallics
catalysts
Catalysts
Intermetallics
hydrogen
partial pressure
Partial pressure
pressure ratio
decoupling
Chemical potential

Keywords

  • Carbon
  • Gallium
  • Intermetallic compound
  • Palladium
  • Selective hydrogenation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Catalysis

Cite this

Armbrüster, M., Behrens, M., Cinquini, F., Föttinger, K., Grin, Y., Haghofer, A., ... Wowsnick, G. (2012). How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry. ChemCatChem, 4(8), 1048-1063. https://doi.org/10.1002/cctc.201200100

How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions : The Role of Subsurface Chemistry. / Armbrüster, Marc; Behrens, Malte; Cinquini, Fabrizio; Föttinger, Karin; Grin, Yuri; Haghofer, Andreas; Klötzer, Bernhard; Knop-Gericke, Axel; Lorenz, Harald; Ota, Antje; Penner, Simon; Prinz, Jan; Rameshan, Christoph; Révay, Zsolt; Rosenthal, Dirk; Rupprechter, Günther; Sautet, Philippe; Schlögl, Robert; Shao, Lidong; Szentmiklósi, L.; Teschner, Detre; Torres, Daniel; Wagner, Ronald; Widmer, Roland; Wowsnick, Gregor.

In: ChemCatChem, Vol. 4, No. 8, 08.2012, p. 1048-1063.

Research output: Contribution to journalArticle

Armbrüster, M, Behrens, M, Cinquini, F, Föttinger, K, Grin, Y, Haghofer, A, Klötzer, B, Knop-Gericke, A, Lorenz, H, Ota, A, Penner, S, Prinz, J, Rameshan, C, Révay, Z, Rosenthal, D, Rupprechter, G, Sautet, P, Schlögl, R, Shao, L, Szentmiklósi, L, Teschner, D, Torres, D, Wagner, R, Widmer, R & Wowsnick, G 2012, 'How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry', ChemCatChem, vol. 4, no. 8, pp. 1048-1063. https://doi.org/10.1002/cctc.201200100
Armbrüster, Marc ; Behrens, Malte ; Cinquini, Fabrizio ; Föttinger, Karin ; Grin, Yuri ; Haghofer, Andreas ; Klötzer, Bernhard ; Knop-Gericke, Axel ; Lorenz, Harald ; Ota, Antje ; Penner, Simon ; Prinz, Jan ; Rameshan, Christoph ; Révay, Zsolt ; Rosenthal, Dirk ; Rupprechter, Günther ; Sautet, Philippe ; Schlögl, Robert ; Shao, Lidong ; Szentmiklósi, L. ; Teschner, Detre ; Torres, Daniel ; Wagner, Ronald ; Widmer, Roland ; Wowsnick, Gregor. / How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions : The Role of Subsurface Chemistry. In: ChemCatChem. 2012 ; Vol. 4, No. 8. pp. 1048-1063.
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