A CeO₂ (100) surface reconstruction unveiled by in situ STEM and particle swarm optimization techniques

The reconstruction of the polar CeO₂ (100) surface has been a subject of long-standing debates due to its complexity and the limited availability of experimental data. Herein, we successfully reveal a CeO₂ (100)-(4 × 6) surface reconstruction by combining in situ spherical aberration-corrected scanning transmission electron microscopy, density functional theory calculations, and a particle swarm optimization-based algorithm for structure searching. We have further elucidated the stabilizing mechanism of the reconstructed structure, which involves the splitting of the filled Ce(4f) states and the mixing of the lower-lying ones with the O(2p) orbitals, as evidenced by the projected density of states. We also reveal that the surface chemisorption properties toward water molecules, an important step in numerous heterogeneous catalytic reactions, are enhanced. These insights into the distinct properties of ceria surface pave the way for performance improvements of ceria in a wide range of applications.