Support-facet-dependent morphology of small Pt particles on ceria

Direct atomic scale information on how the structure of supported nanoparticles is affected by the metal-support interaction is rare. Using scanning transmission electron microscopy, we provide direct evidence of a facet-dependent support interaction for Pt nanoparticles on CeO₂, governing the dimensionality of small platinum particles. Our findings indicate that particles consisting of less than ∼130 atoms prefer a 3D shape on CeO₂(111) facets, while 2D raft structures are favored on CeO₂(100) facets. Measurements of stationary particles on both surface facets are supplemented by time resolved measurements following a single particle with atomic resolution as it migrates from CeO₂(111) to CeO₂(100), undergoing a dimensionality change from 3D to 2D. The intricate transformation mechanism reveals how the 3D particle disassembles and completely wets a neighboring CeO₂(100) facet. Density functional theory calculations confirm the structure-trend and reveal the thermodynamic driving force for the migration of small particles. Knowledge of the presented metal-support interactions is crucial to establish structure-function relationships in a range of applications based on supported nanostructures.