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

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. CeO_x 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.