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Unsubstituted metallophthalocyanine catalysts for the removal of endocrine disrupting compounds using H2O2 as oxidant

DOI:10.1007/s11356-018-3215-4 期刊:Environmental Science and Pollution Research 出版年份:2018 更新时间:2025-09-23 15:22:29
摘要: 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.
作者: Jan Kruid,Ronen Fogel,Janice Limson
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To explore the catalytic activity of water-insoluble metallophthalocyanines (MPc) for the oxidative removal of endocrine disrupting compounds (EDCs) using H2O2 as an oxidant under acidic and neutral conditions, and to compare their efficiency with existing methods.

Water-insoluble metallophthalocyanines, particularly FePc and MnPc, are effective catalysts for the oxidative removal of EDCs using H2O2 under neutral and acidic conditions. FePc showed the highest activity at pH 7, enhanced by acetonitrile and higher H2O2 ratios, while MnPc was active at both pH levels. Over 96% removal of tested EDCs was achieved with lower reagent costs compared to literature methods. This is the first study to report coumestrol removal. Future work should focus on mechanistic studies and application in diverse environmental matrices.

The study is limited to laboratory conditions and specific EDCs; real-world applications may face challenges with catalyst precipitation, matrix effects (e.g., from dam water), and the need for further optimization of reaction conditions. The mechanisms of radical species production and catalyst speciation require additional investigation.

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