Electron transfer to direct oxidation of aqueous organics by perovskites

The residual of oxidant chemicals in advanced oxidation processes(AOPs)resulted in both economic cost and secondary pollution.Herein,we report a direct oxidation of phenolic pollutants induced by Ca-Mn-O perovskites without using an oxidant.Governed by one-electron transfer process(ETP)from the phenolics to the Ca-Mn-O perovskites,this direct oxidation proceeds in fast reaction kinetics with activation energy of 51.4 kJ/mol,which was comparable with those AOPs-based catalytic systems.Additionally,mineralization and polymerization reactions occurred on the Ca-Mn-O surface and ensured the complete removal of phenolics.The high spin state Mn(III)within Ca-Mn-O structure was the dominant active site for this ETP.The elongated axial Mn(III)–O bonds within the[MnO_(6)]octahedron facilitated the acceptance of the electrons from the phenolics and thus promoted the initiation of the direct oxidation process.Mn(III)in the high spin state can also activate dissolved O_(2)to produce singlet oxygen(^(1)O_(2))for a fast removal of phenolics.The mixed Mn(III)/Mn(IV)within Ca-Mn-O accelerated the ETP by enhancing the electrical conductivity.This efficient Ca-Mn-O-induced ETP for removal of organic contaminants casts off the dependence on external chemical and energy inputs and provides a sustainable approach for transforming the toxic organic pollutants into value-added polymers.