A Linear Scaling Relation for CO Oxidation on CeO2-Supported Pd

• DOI: 10.1021/jacs.7b13624
• Publication Date: 2018-03-02T11:14:49Z
• Authors: Jin-Xun Liu; Yaqiong Su; Ivo A. W. Filot; Emiel J. M. Hensen
• Keywords: 01 natural sciences; 0104 chemical sciences

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 Pd8 cluster on ceria (CeO2) in the absence and presence of O2. A Monte Carlo method in the Gibbs ensemble predicts Pd-oxide particles to be stable on CeO2 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 CeO2. This work presents for the first time a scaling relation for a CeO2-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.