Catalytic behavior of the Fe3+/Fe2+ system in the electro-Fenton degradation of the antimicrobial chlorophene

Abstract

The catalytic behavior of the Fe3+/Fe2+ system in the electro-Fenton degradation of the antimicrobial drug chlorophene has been studied considering four undivided electrolytic cells, where a Pt or boron-doped diamond (BDD) anode and a carbon felt or O2-diffusion cathode have been used. Chlorophene electrolyses have been carried out at pH 3.0 under current control, with 0.05M Na2SO4 as supporting electrolyte and Fe3+ as catalyst. In these processes the drug is oxidized with hydroxyl radical (OH) formed both at the anode from water oxidation and in the medium from electrochemically generated Fenton's reagent (Fe2++H2O2, both of them generated at the cathode). The catalytic behavior of the Fe3+/Fe2+ system mainly depends on the cathode tested. In the cells with an O2-diffusion cathode, H2O2 is largely accumulated and the Fe3+ content remains practically unchanged. Under these conditions, the chlorophene decay is enhanced by increasing the initial Fe3+ concentration, because this leads to a higher quantity of Fe2+ regenerated at the cathode and, subsequently, to a greater OH production from Fenton's reaction. In contrast, when the carbon felt cathode is used, H2O2 is electrogenerated in small extent, whereas Fe2+ is largely accumulated because the regeneration of this ion from Fe3+ reduction at the cathode is much faster than its oxidation to Fe3+ at the anode. In this case, an Fe3+ concentration as low as 0.2mM is required to obtain the maximum OH generation rate, yielding the quickest chlorophene removal. Chlorophene is poorly mineralized in the Pt/O2 diffusion cell because the final Fe3+–oxalate complexes are difficult to oxidize with OH. These complexes are completely destroyed using a BDD anode at high current thanks to the great amount of OH generated on its surface. Total mineralization is also achieved in the Pt/carbon felt and BDD/carbon felt cells with 0.2mM Fe3+, because oxalic acid and its Fe2+ complexes are directly oxidized with OH in the medium. Comparing the four cells, the highest oxidizing power regarding total mineralization is attained for the BDD/carbon felt cell at high current due to the simultaneous destruction of oxalic acid at the BDD surface and in the bulk solution.