Time‐Resolved,In Situ DRIFTS/EDE/MS Studies on Alumina‐Supported Rhodium Catalysts: Effects of Ceriation and Zirconiation on Rhodium–CO Interactions |
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| Authors: | Dr. Anna B. Kroner Dr. Mark A. Newton Prof. Dr. Moniek Tromp Dr. Otello M. Roscioni Prof. Andrea E. Russell Prof. Andrew J. Dent Dr. Carmelo Prestipino Prof. John Evans |
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| Affiliation: | 1. Diamond Light Source, Diamond House, Harwell Science and Innovation Campus, Chilton, Oxfordshire, OX11 0DE (UK);2. School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ (UK);3. The European Synchrotron Radiation Facility, 71 Rue des Martyrs, Grenoble, 38043 (France);4. Technische Universit?t München, Lichtenbergstrasse 4, 85748 Garching (Germany);5. Institut des Sciences Chimiques de Rennes, Université de Rennes 1, 35042 Rennes Cedex (France);6. Research Complex at Harwell, Rutherford Appleton Laboratory, Didcot, OX11 1FA (UK) |
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| Abstract: | The effects of ceria and zirconia on the structure–function properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ‐Al2O3) during CO exposure are described. Ceria and zirconia are introduced through two preparation methods: 1) ceria is deposited on γ‐Al2O3 from [Ce(acac)3] and rhodium metal is subsequently added, and 2) through the controlled surface modification (CSM) technique, which involves the decomposition of [M(acac)x] (M=Ce, x=3; M=Zr, x=4) on Rh/γ‐Al2O3. The structure–function correlations of ceria and/or zirconia‐doped rhodium catalysts are investigated by diffuse reflectance infrared Fourier‐transform spectroscopy/energy‐dispersive extended X‐ray absorption spectroscopy/mass spectrometry (DRIFTS/EDE/MS) under time‐resolved, in situ conditions. CeOx and ZrO2 facilitate the protection of Rh particles against extensive oxidation in air and CO. Larger Rh core particles of ceriated and zirconiated Rh catalysts prepared by CSM are observed and compared with Rh/γ‐Al2O3 samples, whereas supported Rh particles are easily disrupted by CO forming mononuclear Rh geminal dicarbonyl species. DRIFTS results indicate that, through the interaction of CO with ceriated Rh particles, a significantly larger amount of linear CO species form; this suggests the predominance of a metallic Rh phase. |
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| Keywords: | analytical methods cerium rhodium supported catalysts zirconium |
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