Revealing the essence of anion ligands in regulating amorphous MnOx to activate peracetic acid for micropollutant removal.

Abstract

How the anion ligands of manganese precursors affect the catalytic activity of amorphous manganese oxides (MnOx) in Fenton-like process is poorly understood. Here, five amorphous MnOx synthesized by Mn(II) precursors with different ligands were characterized and adopted to activate peracetic acid (PAA) for bisphenol A (BPA) degradation. Although > 90 % BPA removal was achieved in the five MnOx/PAA processes via both adsorption and oxidation, the oxidation k_obs greatly differentiates by the ligands types with the order of MnOx-N > MnOx-S > MnOx-Cl > MnOx-AA > MnOx-OA. Ligands types would affect the specific surface area of MnOx and their ability to adsorb BPA, however which is not the decisive factor in determining the contaminant oxidation efficiency. Multiple experimental results indicate that the generation of oxygen vacancies induced by the ligands alters the Mn(III)/Mn(IV) ratio, ultimately contributing to the different efficiency of BPA oxidation driven by the direct electron transfer mechanism. Moreover, amorphous MnOx holds the promise of practical applications in catalytic PAA of various micropollutants with good stability. This study advances the fundamental understanding of ligand-regulated amorphous MnOx-catalyzed PAA process.