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The role of steps in surface catalysis and reaction oscillations

Nature Chemistry volume 2, pages 730–734 (2010)Cite this article

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Abstract

Atomic steps at the surface of a catalyst play an important role in heterogeneous catalysis, for example as special sites with increased catalytic activity. Exposure to reactants can cause entirely new structures to form at the catalyst surface, and these may dramatically influence the reaction by ‘poisoning’ it or by acting as the catalytically active phase. For example, thin metal oxide films have been identified as highly active structures that form spontaneously on metal surfaces during the catalytic oxidation of carbon monoxide. Here, we present operando X-ray diffraction experiments on a palladium surface during this reaction. They reveal that a high density of steps strongly alters the stability of the thin, catalytically active palladium oxide film. We show that stabilization of the metal, caused by the steps and consequent destabilization of the oxide, is at the heart of the well-known reaction rate oscillations exhibited during CO oxidation at atmospheric pressure.

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Figure 1: Spontaneous oscillations in the CO oxidation rate on Pd(001) as measured by SXRD and mass spectrometry.
Figure 2: Stability diagram of the Pd(001) surface measured with SXRD.
Figure 3: Generic model for the reaction rate oscillations.

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Acknowledgements

The authors acknowledge E. Lundgren for providing a palladium crystal and the ESRF staff for support. This work has been financially supported by the Stichting Technische Wetenschappen (STW), the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) and the European Commission under contract no. NMP3-CT-2003-505670 (NANO2).

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Author notes

  1. Salvador Ferrer

    Present address: Present address: CELLS – ALBA, Edifici Ciències Nord. Mòdul C-3 centra, Campus Universitari de Bellaterra, Universita Autònoma de Barcelona, 08193 Bellaterra, Spain,

Authors and Affiliations

  1. Kamerlingh Onnes Laboratory, Leiden University, PO Box 9504, 2300 RA Leiden, The Netherlands

    Bas L. M. Hendriksen, Marcelo D. Ackermann, Richard van Rijn, Dunja Stoltz & Joost W. M. Frenken

  2. European Synchrotron Radiation Facility, 6 rue Jules Horowitz, Grenoble cedex, F-38043, France

    Marcelo D. Ackermann, Richard van Rijn, Ioana Popa, Olivier Balmes, Andrea Resta, Didier Wermeille, Roberto Felici & Salvador Ferrer

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  1. Bas L. M. Hendriksen
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Contributions

B.L.M.H. and J.W.M.F. conceived the new explanation for the oscillatory reaction and B.L.M.H. developed the corresponding numerical model. M.D.A. and I.P. performed the batch experiments. R.v.R., D.S., O.B., A.R. and D.W. performed the flow experiments. M.D.A., R.v.R. and B.L.M.H. analysed the data. R.F. and S.F. supervised the experiments and J.W.M.F. supervised the project. B.L.M.H., M.D.A., R.v.R. and J.W.M.F. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Joost W. M. Frenken.

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The authors declare no competing financial interests.

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Hendriksen, B., Ackermann, M., van Rijn, R. et al. The role of steps in surface catalysis and reaction oscillations. Nature Chem 2, 730–734 (2010). https://doi.org/10.1038/nchem.728

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