Electrochemical oxidation of chlorinated phenols

Electrochemical oxidation has been proposed as a remediation method for chlorinated phenols but is hampered by anode fouling. In this work we explore the mechanism of anode fouling by chlorinated phenols, compare structure vs reactivity for phenols differing in the extent of chlorination, and relate the efficiency of oxidation to the mechanism of oxidation at different electrode types. Linear sweep voltammograms at a Pt anode at several concentrations, sweep rates, and pH were interpreted in terms of deposition of oligomers on the anode surface. Chronopotentiometry at Pt showed that the oxidation potentials of the chlorinated phenol congeners ranged from +0.6 to +1.3 V vs SHE in the pH range 2-12; four electrons are transferred for mono- and trichlorophenols and two for pentachlorophenol. Passivation increased in parallel with the uncompensated resistance of the solution and occurred only at potentials at which water is oxidized, suggesting that the formation of the oligomer film involves attack of hydroxyl radicals on electrochemically oxidized substrate. Seven chlorinated phenols were electrolyzed at PbO2, SnO2, and IrO2 anodes. Relative reactivities of congeners were anode-dependent, due to different mechanisms of oxidation: direct electron-transfer oxidation at PbO2 and hydroxyl radical attack at SnO2 and IrO2. At current densities <0.1 mA cm(-2), current efficiencies >50% could be achieved with 4-chlorophenol at all three anodes.