Selection of active phase of MnO₂ for catalytic ozonation of 4-nitrophenol

Catalytic ozonation is a highly effective method in wastewater treatment, and MnO₂ materials are widely recognized as active heterogeneous catalysts in this process. Many works reported the progress in active MnO₂ synthesis, but the active phase is rarely systematically studied. In this paper, all six phases of MnO₂ (α-, β-, δ-, γ-, λ- and ε-) were synthesized by facile methods. Their catalytic activities in ozonation of 4-nitrophenol (4-NP) were evaluated and correlated with the physicochemical properties obtained from X-ray Diffraction (XRD), transmission electron microscopy (TEM), physical adsorption and cyclic voltammetry (CV) analysis. α- MnO₂ was found to be the most active catalyst in 4-NP degradation at neutral pH. MnO₂ with low average oxidation state (AOS) showed stronger oxidation/reduction peaks in CV characterization, which benefited catalytic decomposition of ozone to generate active species. Superoxide radical was confirmed as the main oxidizing species, along with singlet oxygen and ozone molecule oxidation in bulk solution and little contribution of oxidation on the MnO₂ surface. Mn²⁺ leaching happened during catalytic ozonation, but its catalytic role is negligible. This result may give rise to the preparation of new active MnO₂ catalysts.