Three-year lifetime and regeneration of superoxide radicals on the surface of hybrid TiO2 materials exposed to air

The generation and stabilization of reactive oxygen species (ROS), including the superoxide radical anion (O2-), have a huge potential in environmental remediation and industrial chemical processes, but they still remain a challenge. Here, we elucidate the formation, stability and reactivity of superoxide radicals spontaneously produced on the surface of a hybrid TiO2-acetylacetonate material exposed to air. EPR spectra reveal an exceptional lifetime (up to three years, in air at room temperature) of the adsorbed O2-, which can also be easily regenerated after its decay. The performances of this material in the degradation of organic pollutants in aqueous solution without any light irradiation indicate a heterogeneous catalytic mechanism, mediated by superoxide radicals, with a synergistic homogeneous action of hydroxyl radicals (OH), which are released in solution, as detected by the EPR spin trapping method. The regeneration ability of the adsorbed superoxide radicals by simple exposure to air counteracts the partial instability in aqueous environment of the organic component of the hybrid structure allowing the catalyst reuse. These structural and functional features joined to the simple preparation route open a new perspective in the field of advanced oxidation processes for hybrid TiO2 materials.