Comparative study on CeO2 catalysts with different morphologies and exposed facets for catalytic ozonation: performance, key factor and mechanism insight.

[Display omitted] • The catalytic ozonation performances for seven CeO 2 catalysts with different morphologies and exposed facets are disclosed. • CeO 2 nanorods with (1 1 0) and (1 0 0) facets exposed show the best performance. • A linear relationship between Frenkel-type OV density and O 3 decomposition rate is revealed regardless of morphology and exposed facet. • DFT calculation and experimental data reveal OV boosts O 3 activation on both the Ce and hydroxyl sites of CeO 2. Morphology and facet effects of metal oxides in heterogeneous catalytic ozonation (HCO) are attracting increasing interests. In this paper, the different HCO performances for degradation and mineralization of phenol of seven ceria (CeO 2) catalysts, including four with different morphologies (nanorod, nanocube, nanooctahedron and nanopolyhedron) and three with the same nanorod morphology but different exposed facets, are comparatively studied. CeO 2 nanorods with (1 1 0) and (1 0 0) facets exposed show the best performance, much better than that of single ozonation, while CeO 2 nanocubes and nanooctahedra show performances close to single ozonation. The underlying reason for their different HCO performances is revealed using various experimental and density functional theory (DFT) calculation results and the possible catalytic reaction mechanism is proposed. The oxygen vacancy (OV) is found to be pivotal for the HCO performance of the different CeO 2 catalysts regardless of their morphology or exposed facet. A linear correlation is discerned between the rate of catalytic decomposition of dissolved ozone (O 3) and the density of Frenkel-type OV. DFT calculations and in-situ spectroscopic studies ascertain that the existence of OV can boost O 3 activation on both the hydroxyl (OH) and Ce sites of CeO 2. Conversely, various facets without OV exhibit similar O 3 adsorption energies. The OH group plays an important role in activating O 3 to produce hydroxyl radical (∙OH) for improved mineralization. This work may offer valuable insights for designing Facet- and OV-regulated catalysts in HCO for the abatement of refractory organic pollutants. [ABSTRACT FROM AUTHOR]