A Kinetic Study on the Efficient Formation of High-Valent Mn(TPPS)-oxo Complexes by Various Oxidants

New, more efficient methods of wastewater treatment, which will limit the harmful effects of textile dyes on the natural environment, are still being sought. Significant research work suggests that catalysts based on transition metal complexes can be used in efficient and environmentally friendly processes. In this context, a number of compounds containing manganese have been investigated. A suitable catalyst should have the capacity to activate a selected oxidant or group of oxidants, in order to be used in industrial oxidation reactions. In the present study we investigated the ability of Mn^III(TPPS), where TPPS = 5,10,15,20-tetrakis(4-sulphonatophenyl)-21H,23H-porphyrine, to activate five different oxidants, namely hydrogen peroxide, peracetic acid, sodium hypochlorite, potassium peroxomonosulfate and sodium perborate, via the formation of high valent Mn(TPPS)-oxo complexes. Kinetic and spectroscopic data showed that the oxidation process is highly pH dependent and is strongly accelerated by the presence of carbonate in the reaction mixture for three of the five oxidizing agents. The highest efficiency for the oxidation of Mn^III(TPPS) to high-valent Mn(TPPS)-oxo complexes, was found for peracetic acid at pH ≈ 11 in 0.5 M carbonate solution, which is at least an order of magnitude higher than the rate constants found for the other tested oxidants under similar conditions.