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Structural Analysis of Rh–Pd/CeO2 Catalysts Under Reductive Conditions: An X-ray Investigation

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Abstract

X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) were used to probe the electronic and geometric structures of Rh–Pd/CeO2 catalysts before and after ethanol steam reforming (ESR) at 400 °C, as well as after heating in CO atmospheres as a function of time and temperatures. The O/Ce ratio determined by XPS for the as-prepared Rh–Pd/CeO2 catalysts (individual metal loadings of 0.5 or 2 wt%) were close to 2, with the Rh and Pd present primarily in oxidized form (as oxide and chloride surface species). After ESR at 400 °C the ceria support was heavily reduced to CeO2−x (x = 0.3–0.4), with Rh0 (64 % of total Rh) and Pd0 (67 % of total Pd) being the dominant species. Heating the as-prepared Rh–Pd/CeO2 catalysts under a CO atmosphere at 200–400 °C while monitoring the Pd and Rh K edges by XAS was also conducted. XAS of the K edge of Pd and Rh indicated, as expected, reduction of Pd before that of Rh from 200 °C onward. The FCC order of Pd is however perturbed at 400 °C. On the contrary, Rh once reduced maintained a well ordered (FCC) structure. This observation is rationalised by the greater reduction effect of Pd on CeO2 compared to Rh and therefore at the interface Pd structure may be altered at high temperatures.

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Acknowledgments

This research was undertaken on the XAS beamline at the Australian Synchrotron, Victoria, Australia and the BL01B1 XAFS beamline at the SPring-8 Synchrotron, Hyogo, Japan. The authors are thankful for the beam time and the financial support and Chris Glover, Bernt Johannessen (AS) and Kiyofumi Nitta and Tomoya Uruga (SPring-8) for technical assistance. We thank the Monash Centre for Electron Microscopy, Monash University, Victoria, Australia and the MacDiarmid Institute for Advanced Materials and Nanotechnology, Wellington, New Zealand for their support. MS and TS thank R. Dronskowski and his group (RWTH Aachen University) for the hospitality during our research stay and for all the efforts to make our visit so enjoyable. We also thank the University of Auckland for support of this work through grants-in-aid and travel support.

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Authors and Affiliations

  1. School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland, New Zealand

    M. S. Scott, G. I. N. Waterhouse & T. Söhnel

  2. JASRI/SPring-8, 1-1-1 Kouto, Sayo, Sayou-gun, Hyogo, 679-5198, Japan

    K. Kato

  3. School of Chemistry, Monash University, Melbourne, VIC, 3800, Australia

    S. L. Y. Chang

  4. Saudi Basic Industries Corporation (SABIC), CRI at KAUST, P.O. Box 4545-4700, Thuwal, Saudi Arabia

    H. Idriss

  5. Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study, Massey University, Auckland, New Zealand

    T. Söhnel

  6. Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Peter Grunberg Institute, Forschungszentrum Julich, Julich, 52425, Germany

    S. L. Y. Chang

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  1. M. S. Scott
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  2. G. I. N. Waterhouse
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  3. K. Kato
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  5. H. Idriss
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  6. T. Söhnel
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Correspondence to T. Söhnel.

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Scott, M.S., Waterhouse, G.I.N., Kato, K. et al. Structural Analysis of Rh–Pd/CeO2 Catalysts Under Reductive Conditions: An X-ray Investigation. Top Catal 58, 123–133 (2015). https://doi.org/10.1007/s11244-014-0351-z

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