Cationic Vacancies in Anatase (TiO₂): Synthesis, Defect Characterization, and Ion-Intercalation Properties

As one of the most studied materials, research on titanium dioxide (TiO₂) has flourished over the years owing to technological interest ranging from energy conversion and storage to medical implants and sensors, to name a few. Within this scope, the development of synthesis routes enabling the stabilization of reactive surface structure has been frequently investigated. Among these routes, solution-based synthesis has been utilized to tailor the material's properties spanning its atomic structural arrangement, or morphological aspects. One of the most investigated methods of stabilizing crystals with tailored facets relies on the use of fluoride-based precursors. Fluoride ions not only provide a driving force for the stabilization of metastable/reactive surface structures but also alter the reactivity of titanium molecular precursors and in turn the structural features of the stabilized crystals. Here, we review recent progress in the solution-based synthesis of anatase (one of the polymorphs of TiO₂) employing a fluoride precursor, with an emphasis on how cationic vacancies are stabilized by a charge-compensating mechanism and the resulting structural features associated with these defects. Finally, we will discuss the ion-intercalation properties of these sites with respect to lithium and polyvalent ions such as Mg²⁺ and Al³⁺. We will discuss in more detail the relevant parameters of the synthesis that allow controlling the phase composition with the coexistence of oxide, fluoride, and hydroxide ions within the anatase framework. The mechanism of formation of defective anatase nanocrystals has highlighted a solid-state transformation mostly implying an oxolation reaction (the condensation of hydroxide ions) that results in a decrease in the vacancy content, which can be synthetically controlled. The investigation of local fluorine environments probed by solid-state ¹⁹F NMR revealed up to three coordination modes with different numbers of coordinated Ti⁴⁺ and vacancies. It further revealed the occurrence of single and adjacent pairs of vacancies. These different host sites including native interstitial (and single/paired vacancies) display different ion-intercalation properties. We notably discussed the influence of the local anionic environments of vacancies on the thermodynamics of intercalation properties. The selective intercalation of polyvalent cations such as Mg²⁺ and Al³⁺ further supports the beneficial uses of defect chemistry for developing post-lithium-ion batteries. It is expected that the ability to characterize the local structure of defects is key to the design of unique, tailored-made materials.