Mechanochemical degradation of pentachlorophenol onto birnessite

The existence of a lot of worldwide pentachlorophenol-contaminated sites has induced scientists to concentrate their effort in finding ways to degrade it. Therefore, an effective tool to decompose it from soil mixtures is needed. In this work the efficiency of the phyllomanganate birnessite (KBi) in degrading pentachlorophenol (PCP) through mechanochemical treatments was investigated. To this purpose, a synthesized birnessite and the pollutant were ground together in a high energy mill. The ground KBi-PCP mixtures and the liquid extracts were analyzed to demonstrate that mechanochemical treatments are more efficient in removing PCP than a simple contact between the synthesized birnessite and the pollutant, both in terms of time and extent. The mechanochemically induced PCP degradation mainly occurs through the formation of a surface monodentate inner-sphere complex between the phenolic group of the organic molecules and the structural Mn(IV). This is indicated by the changes induced in birnessite MnO6 layers as a consequence of the prolonged milling with the pollutant. This mechanism includes the Mn(IV) reduction, the consequent formation of Mn(III) and new vacancies, and free Mn2+ ions release. The PCP degradation extent is limited by the presence of chloro-substituents on the aromatic ring.