title: Investigation of the generation of hydroxyl radicals and their oxidative role in the presence of heterogeneous copper catalysts.
abstract: The presence and impact of hydroxyl radicals generated via the catalytic decomposition of H(2)O(2) over heterogeneous copper catalysts were investigated by using two detection methods, an electron spin resonance-spin trapping method and a chemical probe method. Detection of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct signal and formation of 4-chlorocatechol during the oxidation of a 4-chlorophenol substrate demonstrated that the three heterogeneous copper catalysts employed here (CuO, Cu/Al(2)O(3) and CuO.ZnO/Al(2)O(3)) were capable of generating hydroxyl radicals in combination with H(2)O(2). The oxidative mechanism of the hydroxyl radical in the presence of heterogeneous copper catalysts is discussed with regard to the further oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct and hydroxylated products of 4-chlorophenol oxidation. Interestingly, integration of the 5,5-dimethyl-1-pyrroline-N-oxide-OH adduct signal could not be used to reliably measure the total amount of hydroxyl radicals generated as a result of oxidative attack on the adduct. This may be as a result of locally higher hydroxyl radical concentrations in the presence of a heterogeneous catalyst leading to further unwanted oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH.
authors.affiliation: School of Chemical Engineering and Analytical Science, The University of Manchester, Manchester, UK.
authors.forename: J K
authors.initials: JK
authors.lastname: Kim
authors.forename: I S
authors.initials: IS
authors.lastname: Metcalfe
mesh_terms: D000537:Aluminum Oxide / Q000737:chemistry; D002384:Catalysis; D002396:Catechols / Q000032:analysis; D003300:Copper / Q000737:chemistry*; D003497:Cyclic N-Oxides / Q000032:analysis; D004578:Electron Spin Resonance Spectroscopy; D006861:Hydrogen Peroxide / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000032:analysis / Q000737:chemistry*; D016877:Oxidants / Q000032:analysis / Q000737:chemistry*; D010084:Oxidation-Reduction; D018508:Water Purification / Q000379:methods*; D015034:Zinc Oxide / Q000737:chemistry
chemical_list: D002396:Catechols; D003497:Cyclic N-Oxides; D016877:Oxidants; D017665:Hydroxyl Radical; C017245:5,5-dimethyl-1-pyrroline-1-oxide; D003300:Copper; D006861:Hydrogen Peroxide; C038861:4-chlorocatechol; D000537:Aluminum Oxide; D015034:Zinc Oxide; C030973:cupric oxide