Properties of O₂^•^- and OH^• Formed in TiO₂ Aqueous Suspensions by Photocatalytic Reaction and the Influence of H₂O₂ and Some Ions

TLDR

The study examined how H₂O₂ influences O₂•⁻ and OH• generated during TiO₂ photocatalysis using luminol chemiluminescence and terephthalic acid fluorescence probes. Adding H₂O₂ enhances electron‑mediated O₂ reduction, boosts OH• generation, and raises the quantum efficiencies of O₂•⁻ and OH• by 3.0‑ and 3.6‑fold, while the post‑irradiation decay of O₂•⁻ follows fractal‑like kinetics driven by trapped holes.

Abstract

We have investigated the effect of H2O2 on the behavior of O2•- and OH• produced in photocatalysis of aqueous TiO2 suspensions by means of luminol chemiluminescence probing and terephthalic acid fluorescence probing, respectively. The reduction of O2 by photoinduced conduction band electrons (e-) was increased by the addition of H2O2, since the consumption of photoinduced valence band holes (h+) in the oxidation of H2O2 caused the repression of e-−h+ recombination. After the end of the light irradiation, the amount of O2•- decreased based on the fractal-like kinetics at the heterogeneous surface of the TiO2 particle. The decay process might be caused by trapped h+, which cannot react with water and then remains on the TiO2 particle after the irradiation. The energy level of the trapped h+ was estimated to be above the redox potential of SCN-, since it could react with the adsorbed H2O2 and I- ions but not with other ions such as SCN-, Br-, and Cl-. The formation rate of OH• was increased by the addition of H2O2, indicating the direct reduction of adsorbed H2O2 on the TiO2 surface. The quantum efficiencies of the formation of O2•- and OH• were increased by 3.0 and 3.6 times by the addition of 0.2 mM H2O2.