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Visualization of oscillatory behaviour of Pt nanoparticles catalysing CO oxidation

Nature Materials volume 13, pages 884–890 (2014)Cite this article

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Abstract

Many catalytic reactions under fixed conditions exhibit oscillatory behaviour. The oscillations are often attributed to dynamic changes in the catalyst surface. So far, however, such relationships were difficult to determine for catalysts consisting of supported nanoparticles. Here, we employ a nanoreactor to study the oscillatory CO oxidation catalysed by Pt nanoparticles using time-resolved high-resolution transmission electron microscopy, mass spectrometry and calorimetry. The observations reveal that periodic changes in the CO oxidation are synchronous with a periodic refacetting of the Pt nanoparticles. The oscillatory reaction is modelled using density functional theory and mass transport calculations, considering the CO adsorption energy and the oxidation rate as site-dependent. We find that to successfully explain the oscillations, the model must contain the phenomenon of refacetting. The nanoreactor approach can thus provide atomic-scale information that is specific to surface sites. This will improve the understanding of dynamic properties in catalysis and related fields.

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Figure 1: A nanoreactor loaded with Pt nanoparticles catalysing CO oxidation.
Figure 2: Correlation of oscillatory CO oxidation reaction data with the projected morphology of a Pt nanoparticle.
Figure 3: Atomic-scale visualization of the dynamic refacetting of a Pt nanoparticle during the oscillatory CO oxidation.
Figure 4: Microkinetic modelling of CO and O coverage as well as CO oxidation reaction rate on Pt surfaces.

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Acknowledgements

This work was performed in the framework of NIMIC (Nano IMaging under Industrial Conditions), a SmartMix project of the Dutch Ministry of Economic Affairs. The authors acknowledge support from J.C. Wolff and J. van Wingerden (DIMES Technology Centre), G.J.C. van Baarle (Leiden Probe Microscopy BV), and M. Thorhauge and S. Ullmann (Haldor Topsøe A/S). The authors acknowledge Ib Chorkendorff (Technical University of Denmark) for fruitful discussions. Haldor Topsøe A/S is acknowledged for access to its electron microscopy facility. The work is dedicated to the legacy of H. Topsøe and his 100 years of dedication to catalysis and fundamental science.

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Authors and Affiliations

  1. ChemE, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

    S. B. Vendelbo, I. Puspitasari & P. J. Kooyman

  2. Haldor Topsøe A/S, Nymøllevej 55, DK-2800 Kgs. Lyngby, Denmark

    C. F. Elkjær, H. Falsig & S. Helveg

  3. FEI Company, Achtseweg Noord 5, 5651 GG Eindhoven, The Netherlands

    P. Dona & L. Mele

  4. DIMES-ECTM, Delft University of Technology, PO Box 5053, 2600 GB Delft, The Netherlands

    B. Morana & J. F. Creemer

  5. Albemarle Catalyst Company BV, PO Box 37650, 1030 BE Amsterdam, The Netherlands

    B. J. Nelissen

  6. Leiden Probe Microscopy BV, Niels Bohrweg 2, 2333 CA Leiden, The Netherlands

    R. van Rijn

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  1. S. B. Vendelbo
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Contributions

J.F.C., B.M. and L.M. developed and produced the nanoreactors. S.B.V. and P.D. designed and built the specimen holder. S.B.V. and I.P. prepared samples. S.B.V., C.F.E., P.J.K. and S.H. performed the experiments. S.B.V., C.F.E. and S.H. analysed the data. H.F. performed microkinetic modelling. S.B.V. performed reactor simulations. S.H., S.B.V., C.F.E. and H.F. composed the manuscript and it was critically discussed and revised together with J.F.C., P.J.K., B.J.N. and R.R. The project was supervised by S.H.

Corresponding authors

Correspondence to P. J. Kooyman or S. Helveg.

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The authors declare no competing financial interests.

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Vendelbo, S., Elkjær, C., Falsig, H. et al. Visualization of oscillatory behaviour of Pt nanoparticles catalysing CO oxidation. Nature Mater 13, 884–890 (2014). https://doi.org/10.1038/nmat4033

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