Unsubstituted metallophthalocyanine catalysts for the removal of endocrine disrupting compounds using H 2 O 2 as oxidant

Abstract

Advanced oxidation processes have become increasingly important to treat non-biodegradable compounds entering environmental waters. In recent decades, water-soluble metallophthalocyanines have been shown to catalyse H₂O₂-containing oxidation reactions through the production of unique reactive species, nucleophilic metal-peroxo complexes. Few reports in the literature have examined water insoluble metallophthalocyanines (MPc). The oxidative catalytic activity of water insoluble manganese- and iron-phthalocyanine (MnPc, FePc) at pH 7 has been shown through the decolourisation of methylene blue and removal of bisphenol A. These studies expand on this previous study, exploring the catalytic activity of a range of metallophthalocyanines catalysts under both acidic and neutral conditions. FePc, while only active under neutral conditions, was the best performing catalyst. This activity was significantly improved upon by the addition of acetonitrile as a co-solvent, as well as increasing the ratio of H₂O₂ to catalyst. MnPc was catalytically active at both pH 3 and 7. FePc and MnPc catalysts showed the ability to remove bisphenol A in the presence of dam water. Reaction rates were reduced for bisphenol A removal with FePc as a catalyst but were unchanged in the presence of MnPc. The removal of 17β-estradiol, estrone, and coumestrol was successfully demonstrated, with greater than 96% removal of all tested EDC's achieved. This is the first reported study showing the removal of the phytoestrogen, coumestrol. Even though considerably lower concentrations of costly catalysts and oxidation reagents were used in our work, the removal extent of EDC's by the MPc-catalysed oxidation reactions achieved here compares favourably with literature.