Investigating the Unrevealed Photocatalytic Activity and Stability of Nanostructured Brookite TiO2 Film as an Environmental Photocatalyst.

Among three polymorphs of TiO2, the brookite is the least known phase in many aspects of its properties and photoactivities (especially comparable to anatase and rutile) because it is the rarest phase to be synthesized in the standard environment among the TiO2 polymorphs. In this study, we address the unrevealed photocatalytic properties of pure brookite TiO2 film as an environmental photocatalyst. Highly crystalline brookite nanostructures were synthesized on titanium foil using a well-designed hydrothermal reaction, without harmful precursors and selective etching of anatase, to afford pure brookite. The photocatalytic degradation of rhodamine B, tetramethylammonium chloride, and 4-chlorophenol on UV-illuminated pure brookite were investigated and compared with those on anatase and rutile TiO2. The present research explores the generation of OH radicals as main oxidants on brookite. In addition, tetramethylammonium, as a mobile OH radical indicator, was degraded over both pure anatase and brookite phases, but not rutile. The brookite phase showed much higher photoactivity among TiO2 polymorphs, despite its smaller surface area compared with anatase. This result can be ascribed to the following properties of the brookite TiO2 film: (i) the higher driving force with more negative flat-band potential, (ii) the efficient charge transfer kinetics with low resistance, and (iii) the generation of more hydroxyl radicals, including mobile OH radicals. The brookite-nanostructured TiO2 electrode facilitates photocatalyst collection and recycling with excellent stability, and readily controls photocatalytic degradation rates with facile input of additional potential.