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Dynamic in situ observation of rapid size and shape change of supported Pd nanoparticles during CO/NO cycling

Nature Materials volume 6, pages 528–532 (2007)Cite this article

Abstract

Understanding and improving the behaviour of supported precious-metal catalysts for a vast array of environmentally and economically important processes is a central area of research in catalysis. The removal of toxic gases such as CO and NO, without forming others (such as N2O), is particularly important. By combining energy-dispersive extended X-ray absorption fine-structure spectroscopy with a vibrational spectroscopy (infrared) and mass spectrometry, at high time resolution, in a single in situ experiment, we dynamically observe and quantify CO-, and subsequent NO-, induced size and shape changes of Pd nanoparticles during CO/NO cycling. In doing so we demonstrate a novel, non-oxidative redispersion (for example, an increase in metal surface area) mechanism, and suggest a model to bridge the structural and reactive functions of supported Pd catalysts.

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Figure 1: Raw absorption and Fourier-transform representation of Pd K-edge dispersive EXAFS data in three different situations.
Figure 2: Relating Pd–Pd coordination number and the apparent number of atoms per Pd particle during CO/NO cycling.
Figure 3: Correlating structural changes with temporal variations of infrared active adsorbates and CO2 evolution during CO/NO cycling.
Figure 4: A schematic representation of the fundamental steps underlying the reversible, non-oxidative, size (redispersion and sintering) and/or shape changes of Pd nanoparticles during CO/NO cycling.

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Acknowledgements

The authors would like to thank the ESRF for access to facilities and for the funding that permitted the development of this experiment on ID24. T. Mairs, F. Perrin, G. Guilera and A. Kroner are thanked for the various contributions they have made to this work; S. Pascarelli and O. Mathon are thanked for their general support and stewardship of the beamline. Finally, we acknowledge the CYCIT (projects CTQ2004-03409/BQU and CTQ2006-15600/BQU) for financial support. C. Belver thanks the Spanish ‘Ministerio de Educación y Ciencia’ for a ‘Juan de la Cierva’ postdoctoral grant.

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Authors and Affiliations

  1. The European Synchrotron Radiation Facility, 6, Rue Jules Horowitz, BP-220, Grenoble, France

    Mark A. Newton

  2. Instituto de Catalisis y Petroleoquímica, CSIC, C/Marie Curie 2, 28049 Madrid, Spain

    Carolina Belver-Coldeira, Arturo Martínez-Arias & Marcos Fernández-García

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  1. Mark A. Newton
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  2. Carolina Belver-Coldeira
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  3. Arturo Martínez-Arias
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  4. Marcos Fernández-García
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Correspondence to Mark A. Newton or Marcos Fernández-García.

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The authors declare no competing financial interests.

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Supplementary information, table S1 and figures S1-S2 (PDF 161 kb)

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Newton, M., Belver-Coldeira, C., Martínez-Arias, A. et al. Dynamic in situ observation of rapid size and shape change of supported Pd nanoparticles during CO/NO cycling. Nature Mater 6, 528–532 (2007). https://doi.org/10.1038/nmat1924

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