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The properties of Bi-doped lead dioxide electrode were studied in terms of SEM,AFM,XRD and XPS.The electrocatalytic oxidation of nitrophenols (NPs),including mononitrophenols (MNP),dinitrophenols (DNP) and trinitrophenol (TNP) has been studied at Bi-doped lead dioxide anodes on acid medium by cyclic voltammetry and bulk electrolysis.Within the present experimental conditions used (0.36 mmol of nitrophenol L-1,pH 4.3,30 mA cm-2,303 K),the complete decomposition of nitrophenols (NPs) was achieved.The electrochemical oxidation of NPs lay in the order:MNP>DNP>TNP.Molecular configuration as well as the electron character and hydrogen bonds of NPs significantly influenced the electrocatalytic oxidation of these compounds.Intermediates,including hydroquinone,benzoquinone,aminophenols and variety of acids were detected as soluble products during the electrolysis of NPs.Consequently,we proposed possible degradation pathways of these NPs,including the first stage about the release of nitro group from the aromatic rings and subsequent reactions which contained ring fission and formation of a series of carboxylic acids.Finally,all the NPs were oxidized to carbon dioxide and water.