Structural Diversity Design, Four Nucleation Methods Growth and Mechanism of 3D Hollow Box TiO₂ Nanocrystals with a Temperature-Controlled High (001) Crystal Facets Exposure Ratio

Abstract

Three-dimensional (3D) hollow box TiO2 nanocrystals with structural diversity have been designed and grown by four nucleation methods, including the acid dissolution denucleation method with Fe2O3 as heterogeneous nucleation, the topological phase transition method, the sonic solvothermal method, and the air atmosphere sintering method with TiOF2 as homogeneous nucleation. Through full morphology analysis and structural characterization, reasonable growth mechanisms of 3D hollow box TiO2 nanocrystals were proposed, including nucleation dissolution, Oswald ripening, and hydrolysis reactions. It was found that the high energy (001) crystal facets exposure ratio was closely correlated with reaction temperature of four nucleation-methods, which even reached 92% for the first time. Under simulated sunlight irradiation, their hydrogen production performance and photocatalytic degradation efficiency on model dye molecules rhodamine B (RhB) and methylene blue (MB) were evaluated, and as-prepared hollow box TiO2 nanocrystals prepared by the sonic solvothermal method exhibited the best photocatalytic performance, with a hydrogen production rate of 93.88 μmol/g/h. Within 70 min, the photocatalytic degradation rates of RhB and MB reached 96.59 and 75.25%, respectively, which were 5.74 and 5.54 times that of P25. Their properties are closely connected with the orderly cubic and hierarchy configuration structure of hollow box TiO2 nanocrystals, which have a high exposure ratio of (001) facet controlled by reaction temperatures, thereby greatly improving the photocatalytic activity. This study provides a classic reference for improving the properties of hollow box TiO2 nanocrystals through structural diversity design and various methods of nanocrystal growth.