title: Electrochemical oxidation of chlorophenols at a boron-doped diamond electrode and their determination by high-performance liquid chromatography with amperometric detection.
abstract: Anodically pretreated diamond electrodes have been used for the detection of chlorophenols (CPs) in environmental water samples after high-performance liquid chromatographic (HPLC) separation. The anodization of as-deposited boron-doped polycrystalline diamond thin-film electrodes has enabled the stable determination of phenols over a wide concentration range. Prior to the HPLC analysis, a comparative study with ordinary glassy carbon, as-deposited diamond, and anodized diamond was made to examine the oxidative behavior of phenols by cyclic voltammety and flow injection analysis with amperometric detection. At anodized diamond electrodes, reproducible, well-defined cyclic voltammograms were obtained even at high CP concentration (5 mM), due to a low proclivity for adsorption of the oxidation products on the surface. In addition, after prolonged use, the partially deactivated diamond could be reactivated on line by applying a highly anodic potential (2.64 Vvs SCE) for 4 min, which enabled the destruction of the electrodeposited polymer deposits. Hydroxyl radicals produced by the high applied potential, in which oxygen evolution occurs, are believed to be responsible for the oxidation of the passivating layer on the surface. When coupled with flow injection analysis (FIA), anodized diamond exhibited excellent stability, with a response variability of 2.3% (n = 100), for the oxidation of a high concentration (5 mM) of chlorophenol. In contrast, glassy carbon exhibited a response variability of 39.1%. After 100 injections, the relative peak intensity, for diamond decreased by 10%, while a drastic decrease of 70% was observed for glassy carbon. The detection limit obtained in the FIA mode for 2,4-dichlorophenol was found to be 20 nM (S/N = 3), with a linear dynamic range up to 100 microM. By coupling with the column-switching technique, which enabled on-line preconcentration (50 times), the detection limit was lowered to 0.4 nM (S/N = 3). By use of this technique, anodized diamond electrodes were demonstrated for the analysis of CPs in drainwater that was condensed from the flue gas of waste incinerators.
authors.affiliation: Department of Applied Chemistry, School of Engineering, University of Tokyo, Japan.
authors.forename: C
authors.initials: C
authors.lastname: Terashima
authors.forename: Tata N
authors.initials: TN
authors.lastname: Rao
authors.forename: B V
authors.initials: BV
authors.lastname: Sarada
authors.forename: D A
authors.initials: DA
authors.lastname: Tryk
authors.forename: A
authors.initials: A
authors.lastname: Fujishima
mesh_terms: D001895:Boron / Q000737:chemistry*; D002733:Chlorophenols / Q000032:analysis*; D002851:Chromatography, High Pressure Liquid; D018130:Diamond; D004563:Electrochemistry; D004566:Electrodes; D004785:Environmental Pollutants / Q000032:analysis*; D017022:Flow Injection Analysis; D006863:Hydrogen-Ion Concentration
chemical_list: D002733:Chlorophenols; D004785:Environmental Pollutants; D018130:Diamond; D001895:Boron