Regulating oxygen vacancies and hydroxyl groups of α-MnO2 nanorods for enhancing post-plasma catalytic removal of toluene

Although nonthermal plasma (NTP) technology has high removal efficiency for volatile organic compounds (VOCs), it has limited carbon dioxide (CO2) selectivity, which hinders its practical application. In this study, α-MnO2 nanorods with tunable oxygen vacancies and hydroxyl groups were synthesized by two-step hydrothermal process to enhance their activity for deep oxidation of toluene. Hydrochloric acid (HCl) was used to assist in synthesis of α-MnO2 nanorods with tunable oxygen vacancies, furtherly, more hydroxyl groups were introduced to HCl-assisted synthesized α-MnO2 by K+ supplement. The results showed that the as-synthesized nanorods exhibited superior activity, improved by nearly 30% removal efficiency of toluene compared to pristine MnO2 at SIE = 339 J/L, and reaching high COx selectivity of 72% at SIE = 483 J/L, successfully promoting the deep oxidation of toluene. It was affirmed that oxygen vacancies played an important role in toluene conversion, improving the conversion of ozone (O3) and resulting in higher mobility of surface lattice oxygen species. Besides, the enhancement of deep oxidation performance was caused by the increase of hydroxyl groups concentration. In-situ DRIFTS experiments revealed that the adsorbed toluene on catalyst surface was oxidized to benzyl alcohol by surface lattice oxygen, and hydroxyl groups were also found participating in toluene adsorption. Overall, this study provides a new approach to designing catalysts for deep oxidation of VOCs.