A Linear Scaling Relation for CO Oxidation on CeO(2)-Supported Pd

[Image: see text] Resolving the structure and composition of supported nanoparticles under reaction conditions remains a challenge in heterogeneous catalysis. Advanced configurational sampling methods at the density functional theory level are used to identify stable structures of a Pd(8) cluster on ceria (CeO(2)) in the absence and presence of O(2). A Monte Carlo method in the Gibbs ensemble predicts Pd-oxide particles to be stable on CeO(2) during CO oxidation. Computed potential energy diagrams for CO oxidation reaction cycles are used as input for microkinetics simulations. Pd-oxide exhibits a much higher CO oxidation activity than metallic Pd on CeO(2). This work presents for the first time a scaling relation for a CeO(2)-supported metal nanoparticle catalyst in CO oxidation: a higher oxidation degree of the Pd cluster weakens CO binding and facilitates the rate-determining CO oxidation step with a ceria O atom. Our approach provides a new strategy to model supported nanoparticle catalysts.