Effective Toluene Ozonation over δ-MnO₂: Oxygen Vacancy-Induced Reactive Oxygen Species

To improve the reactivity and lifetime of catalysts in the catalytic ozonation of toluene, a simple strategy was provided to regulate the morphology and microstructure of δ-MnO₂ via the hydrothermal reaction temperature. The effects of the reaction temperature and the ozone to toluene concentration ratio on the catalyst performance were investigated. The optimized MnO₂-260 catalyst prepared at the limiting hydrothermal temperature (260 °C) showed high catalytic activity (X_Tol = 95%) and excellent stability (1200 min) at the approximately ambient temperature of 40 °C, which was superior to the results in previous studies. The structure and morphology of δ-MnO₂ were characterized by extended X-ray absorption fine structure, X-ray diffraction, scanning electron microscopy, positron annihilation lifetime spectroscopy, electron spin resonance, and other techniques. Experimental results and density functional theory calculations were in agreement that surface oxygen vacancy clusters, especially surface oxygen dimer vacancies, are critical in ozone activation. Oxygen vacancies can facilitate the adsorption and activation of O₃ to generate reactive oxygen species (ROS, including ¹O₂, O₂^-, and ^•OH), leading to superior ozonation activity to degrade toluene and intermediates. Meanwhile, free radical detection and scavenger tests indicated that ^•OH is the primary ROS during toluene ozonation rather than ¹O₂ or O₂^-.