We are facing a world-wide shortage of clean drinking water which will only be further exacerbated by climate change. The development of reliable and affordable methods for water remediation is thus of utmost importance. Chlorine (which forms active hypochlorites in solution) is the most commonly used disinfectant due to its reliability and low cost. One drawback is that it reacts with organic pollutants to generate toxic chlorinated byproducts. To mitigate chlorination in water remediation, we have investigated the use of catalytic amounts of charged water-soluble iron porphyrins. These are known to activate hypochlorite to generate high valent oxoiron species. We studied the depletion of the model micropollutant phenol and the accumulation of chlorinated disinfection byproducts under water remediation conditions, using iron porphyrins [(TMPyP)FeCl]Cl4 and (NH4)4[(TPPS)FeCl] as catalysts, by membrane inlet mass spectrometry. Despite bearing opposite charges on the meso-substituent, both iron porphyrins suppress the formation of chlorinated disinfection by-products equally well. To gain further insight, spectroscopic studies were performed. These showed the transient formation of Compound II, followed by either regeneration of the iron(III) porphyrin at low NaOCl concentrations, or total decomposition of the porphyrin complex at high NaOCl concentrations. Potential future directions for modifications of porphyrin-based catalysts are discussed.
Keywords: Catalysis; Oxidation; Porphyrins; Water Remediation; iron.
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