Transformation of chlorobenzene by Mn(III) generated in MnO2/organic acid systems.

Chlorobenzene (CB) is a prevalent organic contaminant in water and soil environments. It presents high chemical stability and is resistant to both oxidation and reduction. In this study, we showed that CB was substantially removed by soluble Mn(III) produced during the reductive dissolution of colloidal MnO2 by naturally-occurring organic acids such as formate (FOR), oxalate (OX), and citrate (CIT). The removal rate was dependent on the physicochemical properties of organic acids. With strong electron-donating and coordination ability, OX and CIT promoted MnO2 dissolution and Mn(III) generation compared to FOR, but had adverse effects on the stability and reactivity of Mn(III). As a result, CB removal followed the order: MnO2/CIT > MnO2/FOR > MnO2/OX. Analysis of the transformation products showed that Mn(III) complexes acted as strong electrophiles, attacking the ortho/para carbons of the benzene ring and transforming CB to chlorophenols via an electrophilic substitution mechanism. The theoretical foundation of this proposed reaction mechanism was supplemented by quantum mechanical calculations. Together, the findings of this study provide new insights into the transformation of CB in natural environments and hold the potential to offer a novel strategy for the development of manganese oxide/ligand systems for CB elimination.