Time-Resolved, In Situ DRIFTS/EDE/MS Studies on Alumina-Supported Rhodium Catalysts: Effects of Ceriation and Zirconiation on Rhodium-CO Interactions

• Published in: Chemphyschem 2014-10, Vol.15 (14), p.3049-3059
• Main Authors: Kroner, Anna B., Newton, Mark A., Tromp, Moniek, Roscioni, Otello M., Russell, Andrea E., Dent, Andrew J., Prestipino, Carmelo, Evans, John
• Format: Article
• Language: English
• Subjects: analytical methods; Catalysis; cerium; Chemical Sciences; Chemistry; Exact sciences and technology; General and physical chemistry; Inorganic chemistry; rhodium; supported catalysts; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; zirconium
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201402122

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. Protect the particles! The deposition of zirconia and ceria onto rhodium/alumina by controlled surface modification reactions retards the corrosive chemisorption of the metal by CO‐extruding RhI(CO)2 centers (see picture). For ceria, coordination of cerium to bridging CO on rhodium particles is indicated.