Fluxionality of Au Clusters at Ceria Surfaces during CO Oxidation: Relationships among Reactivity, Size, Cohesion, and Surface Defects from DFT Simulations

Abstract

Density functional theory (DFT) calculations are used to identify correlations among reactivity, structural stability, cohesion, size, and morphology of small Au clusters supported on stoichiometric and defective CeO₂(111) surfaces. Molecular adsorption significantly affects the cluster morphology and in some cases induces cluster dissociation into smaller particles and deactivation. We present a thermodynamic rationalization of these effects and identify Au₃ as the smallest stable nanoparticle that can sustain catalytic cycles for CO oxidation without incurring structural/morphological changes that jeopardize its reactivity. The proposed Mars van Krevelen reaction pathway displays a low activation energy, which we explain in terms of the cluster fluxionality and of labile CO₂ intermediates at the Au/ceria interface. These findings shed light on the importance of cluster dynamics during reaction and provide key guidelines for engineering more efficient metal–oxide interfaces in catalysis