Lewis acids promoted organic pollutants degradation in aqueous solution with peroxymonosulfate and MnO2: New insights into the activation mechanism

Abstract

Nonredox metal ions have been widely recognized to be important in a wide range of biological and chemical oxidations as Lewis acids (LA). However, the role of LA in peroxymonosulfate (PMS) activation for wastewater treatment has not been considered until now. This study shows that oxidizing power of PMS can be promoted after binding nonredox metal ions such as Ca²⁺ as LA, leading to the easier reduction of the oxidant to radicals and substantial enhancement of dye degradation by employing manganese oxides OMS-2 as model catalysts. Increased with Lewis acidity of the metal ion, the rate of PMS decomposition enhanced linearly, while the dye degradation rate first increased and then declined due to the formation of a larger amount of dioxygen. The interactions between Ca²⁺ and PMS were further investigated by Raman, cyclic voltammetry and XPS; and the detailed mechanism of PMS activation was proposed. The performance of Ca²⁺+OMS-2/PMS system under different conditions was also studied. The findings indicate the importance of LA in PMS activation reaction and their role must be considered in other transition metal oxides/PMS systems. It will be also helpful to design new and highly active catalysts for the reactions.

Keywords: Degradation; Lewis acid; Nonredox metal ions; OMS-2; Peroxymonosulfate.