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Journal of Chemical Physics / Volume 135 / Issue 23 / ARTICLES / Gas Phase Dynamics and Structure: Spectroscopy, Molecular Interactions, Scattering, and Photochemistry

J. Chem. Phys. 135, 234303 (2011); http://dx.doi.org/10.1063/1.3669428 (7 pages)

Cooperative effects in the oxidation of CO by palladium oxide cations

Arthur C. Reber1, Shiv N. Khanna1, Eric C. Tyo2, Christopher L. Harmon2, and A. W. Castleman, Jr.2

1Department of Physics, Virginia Commonwealth University, 701 W. Grace St., Richmond, Virginia 23284-2000, USA
2Department of Chemistry and Physics, Pennsylvania State University, 104 Chemistry Research Building, University Park, Pennsylvania 16802, USA

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(Received 26 September 2011; accepted 16 November 2011; published online 19 December 2011)

Cooperative reactivity plays an important role in the oxidation of CO to CO2 by palladium oxide cations and offers insight into factors which influence catalysis. Comprehensive studies including guided-ion-beam mass spectrometry and theoretical investigations reveal the reaction products and profiles of PdO2+ and PdO3+ with CO through oxygen radical centers and dioxygen complexes bound to the Pd atom. O radical centers are more reactive than the dioxygen complexes, and experimental evidence of both direct and cooperative CO oxidation with the adsorption of two CO molecules are observed. The binding of multiple electron withdrawing CO molecules is found to increase the barrier heights for reactivity due to decreased binding of the secondary CO molecule, however, reactivity is enhanced by the increase in kinetic energy available to hurdle the barrier. We examine the effect of oxygen sites, cooperative ligands, and spin including two-state reactivity.

© 2011 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL METHODS
  3. THEORETICAL METHODS
  4. RESULTS
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

adsorption, carbon compounds, catalysis, free radical reactions, mass spectra, molecule-molecule reactions, oxidation, palladium compounds, positive ions

PACS

  • 82.30.Cf

    Atom and radical reactions; chain reactions; molecule-molecule reactions

  • 82.65.+r

    Surface and interface chemistry; heterogeneous catalysis at surfaces

  • 33.15.Ta

    Mass spectra

  • 68.43.Mn

    Adsorption kinetics

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3669428

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    T. Engel and G. Ertl, J. Chem. Phys. 69, 1267 (1978)JCPSA6000069000003001267000001.

    R. E. Leuchtner, A. C. Harms, and A. W. Castleman Jr., J. Chem. Phys. 91, 2753 (1989)JCPSA6000091000004002753000001.

    R. C. Bell, K. A. Zemski, D. R. Justes, and A. W. Castleman Jr., J. Chem. Phys. 114, 798 (2001)JCPSA6000114000002000798000001.

    J. M. L. Martin and A. Sunderman, J. Chem. Phys 114, 3408 (2001)JCPSA6000114000008003408000001.

    J. M. del Campo and A. M. Köster, J. Chem. Phys. 129, 024107 (2008)JCPSA6000129000002024107000001.


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