Comparative study of the electrocatalytic oxidation and mechanism of nitrophenols at Bi-doped lead dioxide anodes

The electrocatalytic oxidation of o-nitrophenol (o-NP), m-nitrophenol (m-NP) and p-nitrophenol (p-NP) has been studied at Bi-doped lead dioxide anodes on acid medium by cyclic voltammetry and bulk electrolysis. The results of voltammetric studies indicated that these nitrophenol isomers were indirectly oxidized by -OH radical in the solutions. Within the present experimental conditions used (50 mg of nitrophenol L-1, pH 4.3, 30 mA cm(-2), 303 K), the complete decomposition of nitrophenols (NPs) was achieved. The electrocatalytic oxidation of NPs lay in the order: p-NP > m-NP > o-NP. Molecular configuration including the electron character and hydrogen bonds of NPs significantly influenced the electrocatalytic oxidation of these isomers. Hydroquinone, catechol, resorcinol, benzoquinone, aminophenols, glutaconic acid and maleic acid and oxalic acid have been detected as soluble products during the electrolysis of NPs. The possible degradation pathways of these isomers were proposed. The first stage is the release of nitro group from the aromatic rings. As a consequence, hydroquinone, catechol, resorcinol and benzoquinone are formed. These organic compounds are oxidized initially to carboxylic acids (glutaconic acid, maleic acid and oxalic acid) and later to carbon dioxide and water. Simultaneously, the reduction of NPs to anninophenols takes place at the cathode. (C) 2008 Elsevier B.V. All rights reserved.