Controllable synthesis and self-template phase transition of hydrous TiO₂ colloidal spheres for photo/electrochemical...

Hydrous TiO₂ colloidal spheres (HTCS) derived from the direct precipitation of titanium alkoxides have attracted continuous interests since 1982. Entering the 21st century, rapid progress in the development of structure-directing agents (SDAs) have enabled reproducible and size-controllable synthesis of highly uniform HTCS with diameters in the nano- to micro-meter range. The availability of various HTCS provides versatile self-templating platforms for the targeted synthesis of nanoporous TiO₂ and titanate spheres with tunable composition, crystallographic phases, and internal structures for a variety of advanced photo/electrochemical applications. This review provides a historical overview for the evolution of HTCS, along with an insightful discussion for the formation mechanism of self-assembly of HTCS during the sol-gel process. Key synthetic parameters including SDA, solvent, reaction temperature and water dosage are discussed for the size and morphology control of HTCS with predictable textural properties. Then, we describe the synthetic strategies of nanoporous TiO₂ and titanate spheres using various HTCS as self-templates. Here, the focus lies on the interactions between TiO₂ nanobuilding blocks with precursors or media at the solid/liquid and solid/solid interfaces, the concurrent phase transitions, and the microstructural and morphological evolutions. Selective formation of crystal phase and internal structures (e.g., solid, hollow, core-shell, yolk-shell) are discussed by manipulating the crystallization kinetics. To further elucidate the composition-structure-property-performance relationship for the resulting nanoporous TiO₂ and titanate spheres, their applications in photo(electro)catalysis, mesoscopic solar cells, and lithium-ion batteries are scrutinized. Finally, we share opinions on key challenges and perspectives for the future controllable preparation, formation mechanisms, and applications of HTCS and their crystalline derivatives.