Carbon Monoxide Oxidation on Ceria-Supported Nanoclusters

Periodic density functional theory is used to evaluate the minimum energy pathways of CO oxidation on cerium oxide-supported platinum and palladium nanoclusters (Pt/CeO2 and Pd/CeO2). For Pt/CeO2, the oxidation process involves the participation of lattice oxygen from CeO2 at the boundary sites of the cluster-ceria interface, which exhibits an exceptionally low energy barrier. Conversely, on Pd/CeO2, oxidation predominantly occurs through oxygen species bound to the Pd cluster. Experimental analysis using the temperature-programmed reduction of the oxidized Pd/CeO2 catalyst reveals a lower CO oxidation temperature compared to Pt/CeO2. This observation aligns with the anticipated decrease in the energy barrier for CO oxidation due to the oxygen coverage of the Pd cluster.