Electrochemical advanced oxidation processes: today and tomorrow. A review

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical (^?OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which ^?OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which ^?OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.     

Enhanced degradation of the antibiotic tetracycline by heterogeneous electro-Fenton with pyrite catalysis

There is actually increasing concern about the accumulation of antibiotics, such as tetracycline, in soil and water bodies. There is therefore a need for efficient methods to degrade antibiotics and thus clean waters. Here we tested the degradation of tetracycline using the heterogeneous electro-Fenton-pyrite method and compared the results with the conventional electro-Fenton method. The reaction was performed with a boron-doped diamond or Pt anode and carbon-felt cathode allowing electrogeneration of H₂O₂ from O₂ reduction. Results show an increasing tetracycline mineralization using the following methods: anodic oxidation with electrogenerated H₂O₂, electro-Fenton and then electro-Fenton-pyrite using boron-doped diamond. Ion-exclusion HPLC revealed the complete removal of malic malonic, succinic, acetic, oxalic and oxamic acids. Nitrogen present in tetracycline was mainly mineralized in NH₄ ⁺. The higher efficiency of electro-Fenton-pyrite is explained by self-regulation of soluble Fe²⁺ and pH to 3.0 from pyrite catalyst favoring larger ^·OH generation from Fenton’s reaction.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

Removal of the herbicide amitrole from water by anodic oxidation and electro-Fenton

Here we demonstrate that an aqueous solution of the herbicide amitrole can be completely depolluted at pH 3.0 by anodic oxidation and electro-Fenton process. Anodic oxidation gives faster degradation with a boron-doped diamond anode than with a Pt anode. Electro-Fenton with a Pt anode and 1 mmol l ^–1 Fe²⁺ as catalyst yields the quickest depollution. Amitrole decay always follows a pseudo first-order reaction. NO₃^– and NH₄⁺ are accumulated in the medium during mineralization, although volatile N-products are also formed. These environmentally friendly electrochemical treatments could be applied to the remediation of wastewaters containing amitrole.     

Electrochemical degradation of the dye indigo carmine at boron-doped diamond anode for wastewaters remediation

Here we demonstrate that anodic oxidation with a boron-doped diamond (BDD) electrode can be applied to the remediation of wastewaters containing indigo carmine. This environmentally friendly method decontaminates completely acid and alkaline aqueous solutions of this dye. The degradation rate increases with increasing current and dye concentration. Indigo carmine is more rapidly removed in alkaline than in acid medium, but its kinetics does not follow a defined reaction order. Isatin 5-sulfonic acid is the main aromatic product formed. Oxalic and oxamic acids are generated as ultimate carboxylic acids. The nitrogen of the dye is converted into NH₄ ⁺ and NO₃ ⁻.     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.