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

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 (CeO2) 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. CeO2 nanorods with (1 1 0) and (1 0 0) facets exposed show the best performance, much better than that of single ozonation, while CeO2 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 CeO2 catalysts regardless of their morphology or exposed facet. A linear correlation is discerned between the rate of catalytic decomposition of dissolved ozone (O3) and the density of Frenkel-type OV. DFT calculations and in-situ spectroscopic studies ascertain that the existence of OV can boost O3 activation on both the hydroxyl (OH) and Ce sites of CeO2. Conversely, various facets without OV exhibit similar O3 adsorption energies. The OH group plays an important role in activating O3 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.