Enhanced MnO₂ oxidation of methotrexate through self-sensitized photolysis

MnO₂, which is ubiquitous in soil and sediment in natural water environments, may play an important role in the photolysis of contaminants by sunlight, but the interactions between MnO₂ and contaminants in aqueous environments under sunlight irradiation have not been investigated. In this study, the simultaneous presence of sunlight and MnO₂ significantly enhanced the degradation efficiency of methotrexate (MTX). Accordingly, we hypothesized that the overall enhancement of this synergistic reaction is due to the additional production of Mn(III) via MTX self-sensitized photolysis. The pseudo-first-order kinetic model for the photoreaction of MTX with MnO₂ (Light/MTX+MnO₂) during the initial reaction kinetics (0-2 h) revealed a rate constant of 0.43 h¹ ([MTX] = 20 μM, [MnO₂] = 200 μM, and pH = 7), which is faster than that obtained with sunlight alone (0.14 h¹) or MnO₂ alone; Mn(II) and Mn(III) were formed at concentrations of 24.3 ± 1.0 μM and 14.8 ± 1.4 μM, respectively. Dissolved Mn(III) species were identified as the main oxidant species responsible for the degradation of MTX. Two reaction pathways for the production of Mn(III) through Light/MTX+MnO₂ were proposed; MTX acts as a photosensitizer to produce ³MTX* responsible for the reduction of MnO₂ to Mn(III), whereas O₂^• participates in the oxidation of Mn(Ⅱ) to Mn(Ⅲ). Byproduct analysis demonstrated that the Mn(III) generated in the Light/MTX+MnO₂ system enhances C－N bond cleavage, ketonization, and hydrolysis pathways in the MTX transformation.