Surface Refaceting Mechanism on Cubic Ceria

Polar surfaces of solid oxides are intrinsically unstable and tend to reconstruct due to the diverging electrostatic energy and thus often exhibit unique physical and chemical properties. However, a quantitative description of the restructuring mechanism of these polar surfaces remains challenging. Here we provide an atomic-level picture of the refaceting process that governs the surface polarity compensation of cubic ceria nanoparticles based on the accurate reference data acquired from the well-defined model systems. The combined results from advanced infrared spectroscopy, atomic-resolved transmission electron microscopy, and density functional theory calculations identify a two-step scenario where an initial O-terminated (2 × 2) reconstruction is followed by a severe refaceting via massive mass transport at elevated temperatures to yield {111}-dominated nanopyramids. This significant surface restructuring promotes the redox properties of ceria nanocubes, which account for the enhanced catalytic activity for CO oxidation.