The Virtue of Defects: Stable Bromine Production by Catalytic Oxidation of Hydrogen Bromide on Titanium Oxide

Rutile TiO₂ is a heavily investigated oxide with, to date, scarce applications in industrial catalysis. The inactivity of this material in oxidations has been related to its inability to dissociate molecular oxygen. Herein we show how rutile catalyzes the oxidation of HBr to Br₂ through defect states that are introduced during the reaction. The identification of active, stable, and abundant materials for bromine production is key to the future implementation of Br₂‐mediated alkane functionalization processes. The catalytic properties of TiO₂ are discussed in comparison to expensive rutile‐type oxides, such as RuO₂ and IrO₂, on the basis of surface characterization and molecular modeling.