Superoxide radical-induced rapid valence cycling of Mn(II/III/IV) for efficient degradation of organic pollutants

Abstract

Transition metal oxides are one of the commonly used catalysts for ozone oxidation, and the slow redox cycling of different valence metal components inside the catalysts currently becomes a key bottleneck limiting their catalytic activity. In this work, the superoxide radicals generated at the N/C sites were used to reduce the neighboring high-valence metal components to low-valence states to construct a new mechanism for the rapid cyclic transition of Mn (II/III/IV) valence states. What's more, N/C sites enhanced the ozone adsorption and conversion ability, synergized with the adjacent MnO2 sites to generate interfacial hydroxyl radicals and superoxide radicals, and effectively inhibited the quenching effect of inorganic salt ions (e.g., Cl-, SO42-) on the free radicals. For the actual printing and dyeing wastewater, the COD (chemical oxygen demand) removal rate was as high as 70 % in 60 min and remained stable in 10 cycles with almost no manganese ions leaching. In addition, characterization such as EPR combined with DFT calculations showed that the dual-site structure significantly increased the oxygen vacancy content and Lewis acidity, and the synergistic interaction between graphite N and MnO2 was the most favorable for ozone conversion with the lowest reaction energy barriers.