The increased oxygen vacancy by morphology regulation of MnO₂ for efficient removal of PAHs in aqueous solution

Manganese dioxide (MnO₂) is considered to have a promising future in degrading polycyclic aromatic hydrocarbons (PAHs) in aqueous phase because of its low cost and environmental friendliness. In this study, various MnO₂ morphologies were prepared, and their removal performance and mechanism were evaluated using benzo(a)pyrene (B[a]P) as model molecule. Results showed that nanoflower MnO₂ with higher concentration of oxygen vacancies exhibited better oxidative and easier oxygen migration properties, and thus enhanced PAHs removal by 14.28%-43.21% compared with other MnO₂ samples. Additionally, the transformation rate of PAHs is correlated with their ionization potential (IP) values. Further mechanism studies showed that the degradation of B[a]P by MnO₂ process was first to form a combination and then oxidized by non-radical Mn species and superoxide radical (O₂^-•) to produce degradation product (B[a]P-6-one and B[a]P-6,12-quinone). The specific surface area was not the main factor affecting the removal of B[a]P by MnO₂ and oxidation was the main removal mechanism of degrading B[a]P by MnO₂. Mn³⁺ and absorbed oxygen (O_abs) played an important role in the process of removing PAHs by MnO₂. Additionally, synergistic effects of oxygen vacancy and Mn³⁺could be benefit for transforming O_abs to O₂^-•, leading to the efficient degradation of PAHs.