Evolution of Ce4+ Lewis acidity during dehydroxylation of ceria nanoparticles with different morphology: An integrated FTIR, DFT and HRTEM study

Ceria is an important redox catalyst and its activity depends on the open Ce4+/Ce3+ sites, anion vacancies, surface OH groups and the ratio between them. We investigated the effect of dehydroxylation on the evolution of Ce4+ Lewis acidity of oxidized ceria nanocubes, nanopolyhedra, and nanorods. The {1 1 1} face is not hydroxylated and the exposed Ce4+ sites, after dehydration, adsorb CO weakly, forming linear carbonyls. The hydroxyl coverage of the {1 1 0} face consists of terminal and bridging hydroxyls, and dehydroxylation occurs between 423 and to 573 K by interaction between these groups. The produced Ce4+ sites form stronger linear carbonyls. The {1 0 0} face is covered by bridging OH groups, which are progressively removed even at 773 K. The created Ce4+ sites coordinate CO in a bridging mode and, at higher coverage, connect two bridging CO molecules. Ce4+ sites on edges and defects appear at high evacuation temperature and form mono- and dicarbonyls.