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Particle size effects in Rh/Al2O3 catalysts as viewed from a structural, functional, and reactive perspective: the case of the reactive adsorption of NO

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Abstract

The structural-dynamic behaviour of γ-Al2O3 supported Rh nanoparticles under He, H2/He, and NO/He has been investigated using a newly developed methodology that permits dispersive EXAFS (EDE), diffuse reflectance infra red spectroscopy (DRIFTS), and mass spectrometry (MS) to be applied simultaneously to the study of gas-solid interactions. This reveals a considerably variability in nanoparticle habit (for 11 Å diameter nanoparticles as a function of temperature), and between 8 Å and 11 Å particles in their response to NO. The selectivity (N2/(N2 + N2O)) of the reactive interaction between NO and the supported Rh shows essentially no particle size dependence above 473 K: it is apparent, however, that considerable differences in some aspects of the structural behaviour of the 8 Å and 11 Å Rh particles do nonetheless, exist. At 373 < T < 473 K a clear divergence in structural, functional, and reactive response of the different sized supported Rh nanoparticles toward NO is observed. These observations are discussed in terms of the ability of different sized Rh particles to change structure in response to the reactive environment, the subsequent effect this has on the nitrosyl functionality that different phases may support, and the reactive pathways for NO conversion that may therefore arise.

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Acknowledgements

This work was funded by the EPSRC UK (Grant Number GR/60744/01) and the authors thank the EPSRC for the provision of post doctoral and PhD funding to MAN and BJ respectively. The ESRF are thanked for the provision of facilities within a long-term proposal awarded for this research. John James (University of Southampton), and Florian Perrin (ESRF) are gratefully acknowledged for their technical contributions to this work. Dr Gordon McDougall is also greatly thanked for the technical schematics of a novel DRIFTS cell designed and constructed at the department of chemistry, University of Edinburgh, Scotland. MAN would further like to thank the directors of the ESRF for funding for the continued development and implementation of this methodology at the ESRF for the wider use of the scientific community.

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Authors and Affiliations

  1. The European Synchrotron Radiation Facility, 38043, Grenoble, France

    Mark A. Newton

  2. Diamond Light Source, Chilton, Oxford, UK

    Andrew J. Dent & John Evans

  3. Synchrotron Radiation Source, Daresbury, Warrington, UK

    Steven G. Fiddy

  4. School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

    Bhrat Jyoti & John Evans

Authors
  1. Mark A. Newton
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  2. Andrew J. Dent
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  3. Steven G. Fiddy
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  4. Bhrat Jyoti
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  5. John Evans
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Correspondence to Mark A. Newton.

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Newton, M.A., Dent, A.J., Fiddy, S.G. et al. Particle size effects in Rh/Al2O3 catalysts as viewed from a structural, functional, and reactive perspective: the case of the reactive adsorption of NO. J Mater Sci 42, 3288–3298 (2007). https://doi.org/10.1007/s10853-006-0751-y

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