Electrochemistry for the Environment

pp 515-552


Use of Both Anode and Cathode Reactions in Wastewater Treatment

  • Enric BrillasAffiliated withLaboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona Email author 
  • , Ignasi Sirés
  • , Pere Lluı́s Cabot

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Here, we describe the fundamentals, laboratory experiments, and environmental applications of indirect electrooxidation methods based on H2O2 electrogeneration such as electro-Fenton, photoelectro-Fenton and peroxicoagulation for the treatment of acidic wastewaters containing toxic and recalcitrant organics. These methods are electrochemical advanced oxidation processes that can be used in divided and undivided electrolytic cells in which pollutants are oxidized by hydroxyl radical (OH) produced from anode and/or cathode reactions. H2O2 is generated from the two-electron reduction of O2 at reticulated vitreous carbon, graphite, carbon-felt, and O2-diffusion cathodes. The most usual method is electro-Fenton where Fe2 + added to the wastewater reacts with electrogenerated H2O2 to yield OH and Fe3 + from Fenton’s reaction. An advantage of this technique is that Fe2 + is continuously regenerated from cathodic reduction of Fe3 +. The characteristics of different electro-Fenton systems where pollutants are simultaneously destroyed by OH formed in the medium from Fenton’s reaction and at the anode surface from water oxidation are explained. The effect of the anode [Pt or boron-doped diamond (BDD)] and cathode (carbon-felt or O2-diffusion) on the degradation rate of persistent industrial by-products, herbicides, pharmaceuticals, dyes, etc. is examined. Initial pollutants react much more rapidly with OH formed in the medium and their degradation sequences are discussed from aromatic intermediates and finally short aliphatic acids are detected. The synergetic positive catalytic effect of Cu2 + on the electro-Fenton process is evidenced. The photoelectro-Fenton method involves the irradiation of the wastewater with UVA light that rapidly photodecomposes complexes of Fe3 + with final carboxylic acids enhancing total decontamination. The peroxicoagulation method uses a sacrificial Fe anode that is continuously oxidized to Fe2 + and organics are either mineralized with OH formed from both electrogenerated Fe2 + and H2O2 or removed by parallel coagulation with the FeOH3 precipitate formed from the excess of Fe3 + generated from Fenton’s reaction.