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.

Traditional physicochemical and biological techniques, as well as advanced oxidation processes (AOPs), are often inadequate, ineffective, or expensive for industrial water reclamation. Within this context, the electrochemical technologies have found a niche where they can become dominant in the near future, especially for the abatement of biorefractory substances. In this critical review, some of the most promising electrochemical tools for the treatment of wastewater contaminated by organic pollutants are discussed in detail with the following goals: (1) to present the fundamental aspects of the selected processes; (2) to discuss the effect of both the main operating parameters and the reactor design on their performance; (3) to critically evaluate their advantages and disadvantages; and (4) to forecast the prospect of their utilization on an applicable scale by identifying the key points to be further investigated. The review is focused on the direct electrochemical oxidation, the indirect electrochemical oxidation mediated by electrogenerated active chlorine, and the coupling between anodic and cathodic processes. The last part of the review is devoted to the critical assessment of the reactors that can be used to put these technologies into practice.

The electrogeneration of hydroxyl radicals was studied at a synthetic boron-doped diamond ͑BDD͒ thin film electrode. Spin trapping was used for detection of hydroxyl radicals with 5,5-dimethyl-1-pyrroline-N-oxide and with salicylic acid using electron spin resonance and liquid chromatography measurements, respectively. The production of hydrogen peroxide and competitive oxidation of formic and oxalic acids were also investigated using bulk electrolysis. The results have shown that oxidation of salicylic acid leads to the production of hydroxylated products ͑2,3and 2,5-dihydroxybenzoic acids͒. These results demonstrate that the oxidation process on BDD electrodes involves hydroxyl radicals as electrogenerated intermediates.

The electrochemical behavior of synthetic boron-doped diamond thin-film electrode ͑BDD͒ has been studied in acid media containing 4-chlorophenol ͑4-CP͒ by cyclic voltammetry, chronoamperometry, and bulk electrolysis. The results have shown that in the potential region of supporting electrolyte stability occur reactions involving the oxidation of 4-CP to phenoxy radical and 1,4-benzoquinone. Polymeric materials, which result in electrode fouling, are also formed in this potential region. Electrolysis at high anodic potentials, in the region of electrolyte decomposition, complex oxidation reactions can take place involving electrogenerated hydroxyl radicals, leading to the complete incineration of 4-chlorophenol. Electrode fouling is inhibited under these conditions. The experimental results have been also compared with a theoretical model. This model is based on the assumption that the rate of the anodic oxidation of 4-CP is a fast reaction. Finally, high-pressure liquid chromatographic analyses revealed that the main intermediate products of 4-CP oxidation were 1,4-benzoquinone, maleic acid, formic acid, and oxalic acid.

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