Volatile organic compound removal by post plasma-catalysis over porous TiO₂ with enriched oxygen vacancies in a dielectric barrier discharge reactor

Non-thermal plasma (NTP) degradation of volatile organic compounds (VOCs) into CO₂ and H₂O is a promising strategy for addressing ever-growing environment pollution. However, its practical implementation is hindered by low conversion efficiency and emissions of noxious by-products. Herein, an advanced low-oxygen-pressure calcination process is developed to fine-tune the oxygen vacancy concentration of MOF-derived TiO₂ nanocrystals. Vo-poor and Vo-rich TiO₂ catalysts were placed in the back of an NTP reactor to convert harmful ozone molecules into ROS that decompose VOCs via heterogeneous catalytic ozonation processes. The results indicate that Vo-TiO₂-5/NTP with the highest Vo concentration exhibited superior catalytic activity in the degradation of toluene compared to NTP-only and TiO₂/NTP, achieving a maximum 96% elimination efficiency and 76% CO_x selectivity at an SIE of 540 J L⁻¹. Mechanistic analysis reveals that the ¹O₂, ˙O₂⁻ and ˙OH species derived from the activation of O₃ molecules on Vo sites contribute to the decomposition of toluene over the Vo-rich TiO₂ surface. With the aid of advanced characterization and density functional theory calculations, the roles of oxygen vacancies in manipulating the synergistic capability of post-NTP systems were explored, and were attributed to increased O₃ adsorption ability and enhanced charge transfer dynamics. This work presents novel insights into the design of high-efficiency NTP catalysts structured with active Vo sites.