Advances in the synthesis of pure brookite and brookite-based TiO2 materials have opened the way to fundamental and applicative studies of the once least known TiO2 polymorph. Brookite is now recognized as an active phase, in some cases showing enhanced performance with respect to anatase, rutile or their mixture. The peculiar structure of brookite determines its distinct electronic properties, such as band gap, charge–carrier lifetime and mobility, trapping sites, surface energetics, surface atom arrangements and adsorption sites. Understanding the relationship between these properties and the photocatalytic performances of brookite compared to other TiO2 polymorphs is still a formidable challenge, because of the interplay of many factors contributing to the observed efficiency of a given photocatalyst. Here, the most recent advances in brookite TiO2 material synthesis and applications are summarized, focusing on structure/activity relation studies of phase and morphology-controlled materials. Many questions remain unanswered regarding brookite, but one answer is clear: Is it still worth studying such a hard-to-synthesize, elusive TiO2 polymorph? Yes.
