Transformation of TiOF₂ Cube to a Hollow Nanobox Assembly from Anatase TiO₂ Nanosheets with Exposed {001} Facets via Solvothermal Strategy

Hierarchical nanostructures have attracted increasing interest due to their exceptional properties and widespread potential applications. In this paper, anatase TiO2 hollow nanoboxes (TiO2-HNBs) are formed by assembly of nanosheets with exposed {001} facets by solvothermal treatment of TiOF2 cubes in alcohols (tert-butanol and ethanol) at 180 °C. It was found that phase transformation of TiOF2 to anatase TiO2 begins at corners and edges of TiOF2 cubes due to in situ hydrolysis of TiOF2, where water was produced by dehydration of alcohol molecules. With extension the reaction time, TiO2-HNB assemblies from nanosheets with exposed high-energy {001} facets were formed due to the steady inside-outside dissolution-recrystallization process. However, the resulting hierarchical TiO2-HNBs are unstable, which can decompose to discrete high-energy TiO2 nanosheets if the reaction time is further extended. The hierarchical TiO2-HNBs show higher photocatalytic activity than discrete high-energy TiO2 nanosheets and P25 TiO2 due to the unique structures of TiO2-HNBs.