- Oxidative degradation of toxic organic pollutants by water soluble nonheme iron(iv)-oxo complexes of polydentate nitrogen donor ligands
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The ability of four mononuclear nonheme iron(iv)-oxo complexes supported by polydentate nitrogen donor ligands to degrade organic pollutants has been investigated. The water soluble iron(ii) complexes upon treatment with ceric ammonium nitrate (CAN) in aqueous solution are converted into the corresponding iron(iv)-oxo complexes. The hydrogen atom transfer (HAT) ability of iron(iv)-oxo species has been exploited for the oxidation of halogenated phenols and other toxic pollutants with weak X-H (X = C, O, S,etc.) bonds. The iron-oxo oxidants can oxidize chloro- and fluorophenols with moderate to high yields under stoichiometric as well as catalytic conditions. Furthermore, these oxidants perform selective oxidative degradation of several persistent organic pollutants (POPs) such as bisphenol A, nonylphenol, 2,4-D (2,4-dichlorophenoxyacetic acid) and gammaxene. This work demonstrates the utility of water soluble iron(iv)-oxo complexes as potential catalysts for the oxidative degradation of a wide range of toxic pollutants, and these oxidants could be considered as an alternative to conventional oxidation methods.
- Jana, Rahul Dev,Munshi, Sandip,Paine, Tapan Kanti
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p. 5590 - 5597
(2021/05/04)
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- Electroreductive dechlorination of α-hexachlorocyclohexane catalyzed by iron porphyrins in nonaqueous media
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Two iron porphyrins, (TPP)FeCl and (OEP)FeCl, where TPP and OEP are the dianions of tetraphenylporphyrin and octaethylporphyrin, respectively, were utilized as catalysts for the electroreductive dechlorination of α-hexachlorocyclohexane (α-HCH) which was monitored by electrochemistry, in situ UV-visible spectroelectrochemistry and controlled potential electrolysis in N,N′-dimethylformamide. GC-MS analysis of the α-HCH degradation products revealed the stepwise formation of pentachlorocyclohexene and tetrachlorocyclohexadiene as intermediates, prior to generation of the final dechlorination products which consisted of an isomeric mixture of trichlorobenzenes. Based on identification of the intermediates and final products in the reaction, an overall dechlorination mechanism of α-hexachlorocyclohexane is proposed.
- Zhu, Weihua,Ni, Cui,Liang, Lili,Li, Junwen,Li, Minzhi,Ou, Zhongping,Kadish, Karl M.
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p. 519 - 527
(2014/07/21)
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- Photocatalytic degradation of lindane by polyoxometalates: Intermediates and mechanistic aspects
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The photocatalytic degradation of lindane (γ-1,2,3,4,5,6-hexachlorocyclohexane) has been studied in the presence of the polyoxometalate PW12O403- in aqueous solutions. Lindane is fully decomposed to CO2, Cl- and H2O, while a great variety of intermediates has been detected using GC-MS, including aromatic compounds (dichlorophenol, trichlorophenols, tetrachlorophenol, hexachlorobenzene, di- and trichloro-benzenodiol), non-aromatic cyclic compounds (penta-, tetrachlorocyclohexene, heptachlorocyclohexane), aliphatic compounds (tetrachloroethane) and condensation products (polychlorinated biphenyls). The number and nature of the intermediates implies that the mechanism of decomposition of lindane is based on both oxidative and reductive processes. Common intermediates have been reported during photolysis of lindane in the presence of titanium dioxide. A similar overall mechanism of polyoxometalates and TiO2 photocatalysis through the formation of common reactive species is suggested.
- Antonaraki,Triantis,Papaconstantinou,Hiskia
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experimental part
p. 119 - 124
(2010/08/22)
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