Carlos A. Martínez-Huitle

Electrochemical measurements and theoretical studies for understanding the behavior of catechol, resorcinol and hydroquinone on the boron doped diamond surface

Using electrochemical techniques (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)) with a boron-doped diamond (BDD) electrode it was possible to study the behavior of hydroquinone (HQ), catechol (CT) and resorcinol (RS), in aqueous solutions as well as to associate the electrochemical profiles with computational simulations. It led to understanding the factors that influence the direct electrooxidation of HQ, CT and RS on the BDD surface. Theoretical calculations demonstrated that the compounds with lower HOMO energy and high ionization potential (IP) are more stable, showing a higher Epa, denoting that HOMO energies and IP are related to the difficulty of oxidizing (losing an electron) a specific compound. Analyzing the electro-oxidation reactions of HQ, CT and RS by using computational calculations, it was possible to verify the reversibility behavior, direct oxidation pathway and the possible intermediates formed during electron-transfer. The results clearly demonstrated that the reversibility was attained for HQ and CT, while this behavior is not feasible, thermodynamically speaking, for RS and this was confirmed by DFT calculations. For direct oxidation mechanisms, HQ and CT are quickly oxidized, but RS produces stable intermediates. These experimental and theoretical results also explain the behavior when the compounds were analyzed by electroanalytical techniques, suggesting that the interactions by direct electron-transfer determine the stability of response (sensitivity) as well as the limit of detection. The results are described and discussed in light of the existing literature.

Evidence for the electrochemical production of persulfate at TiO2 nanotubes decorated with PbO2

It is well known that PbO2-based electrodes are considered to be non-active anodes, producing higher concentrations of hydroxyl radicals in aqueous solutions, and consequently, favouring the electrochemical degradation of organic pollutants. However, no evidence has been reported on the production of persulfates using this kind of electrode in sulphate aqueous solutions. For this reason, the aim of this work is to prepare (by an electrochemical procedure (anodization and electrodeposition)) and characterize (by X-ray diffraction, scanning electron microscopy, and potentiodynamic measurements) Ti/TiO2-nanotubes/PbO2 disk electrodes (with a geometrical area of 65 cm2) in order to evaluate the electrochemical production of persulfate using Na2SO4 solution as the support electrolyte and applying current densities of 7.5 and 60 mA cm−2, as well as the influence of the electrosynthesis of hydroxyl radicals, in concomitance. The results clearly showed that significant production of hydroxyl radicals and persulfate is achieved at the Ti/TiO2-nanotubes/PbO2 surface, but this depends on the current density. The production of ˙OH at the Ti/TiO2-nanotubes/PbO2 surface in Na2SO4 solution was confirmed by a RNO spin trapping reaction. The results were compared with those of a Ti/Pt electrode in order to understand the effect when a lower amount of ˙OH is produced at the active anode surface. Based on the results, the Ti/TiO2-nanotubes/PbO2 anode could exhibit good electrocatalytic properties for environmental applications involving persulfate oxidants.

Electrochemical advanced oxidation processes as decentralized water treatment technologies to remediate domestic washing machine effluents

Water scarcity is one of the major concerns worldwide. In order to secure this appreciated natural resource, management and development of water treatment technologies are mandatory. One feasible alternative is the consideration of water recycling/reuse at the household scale. Here, the treatment of actual washing machine effluent by electrochemical advanced oxidation processes was considered. Electrochemical oxidation and electro-Fenton technologies can be applied as decentralized small-scale water treatment devices. Therefore, efficient decolorization and total organic abatement have been followed. The results demonstrate the promising performance of solar photoelectro-Fenton process, where complete color and organic removal was attained after 240xa0min of treatment under optimum conditions by applying a current density of 66.6xa0mAxa0cm−2. Thus, electrochemical technologies emerge as promising water-sustainable approaches.

Towards Sustainability: Photochemical and Electrochemical Processes Applied for Environmental Protection

Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, km 14.5 Carr. Toluca-Atlacomulco, Universidad Autónoma del Estado de México, Toluca, MEX 50200, Mexico Universidade Federal do Rio Grande do Norte, Campus Universitário s/n, Lagoa Nova, 59078-970 Natal, Brazil Unesp, National Institute for Alternative Technologies of Detection, Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT-DATREM), Institute of Chemistry, P.O. Box 355, 14800-900 Araraquara, SP, Brazil Universidad Nacional de Ingeniería, Av. Tupac Amaru 210, Lima, Peru

Electrochemical advanced oxidation processes (EAOPs) as alternative treatment techniques for carwash wastewater reclamation

Electrochemical advanced oxidation processes such as electrooxidation (EO), electrooxidation with hydrogen peroxide generation (EO-H2O2) and electro-Fenton process (EF) have been investigated as alternative treatment techniques for complete removal of anionic surfactants and organic matters from real carwash wastewater. The electrochemical processes were performed with acidified real carwash wastewater using boron doped anode and carbon felt cathode. In all cases, the chemical oxygen demand (COD) removal efficiency was always increased with rise in applied current and complete organic matter decay was achieved at applied current of 500u202fmA or above after 6u202fh of electrolysis. Faster and higher COD decay was observed with EF compared to either EO or EO-H2O2 treatment, at all currents and electrolysis time. Besides, complete degradation of anionic surfactants - the major organic content of the wastewater could be achieved at all applied currents studied irrespective of the process used, indicating the efficacy of processes for total remediation of real carwash wastewater. The short-chain carboxylic acids formed as the final organic byproducts were identified and quantified by ion-exclusion chromatography. More so, lower energy consumption and higher current efficiency were achieved with EF compared to EO-H2O2. Electrochemical treatment was found to be a powerful technology for the complete abatement of organic matter in carwash wastewater for possible reuse.

Improving the catalytic effect of peroxodisulfate and peroxodiphosphate electrochemically generated at diamond electrode by activation with light irradiation

Boron doped diamond (BDD) anode has been used to oxidatively remove Rhodamine B (RhB), as persistent organic pollutant, from synthetic wastewater by electrolysis, photoelectrolysis and chemical oxidation containing sulfate and phosphate as supporting electrolytes. RhB is effectively oxidized by electrolysis and by chemical oxidation with the oxidants separately produced by electrolyzing sulfate or phosphate solutions (peroxodisulfate and peroxodiphosphate, respectively). The results showed that light irradiation improved the electrolysis of RhB due to the activation of oxidants under irradiation at high current densities. Meanwhile, the efficiency of the chemical oxidation approach by ex situ electrochemical production of oxidants was not efficient to degrade RhB.

Functional group influences on the reactive azo dye decolorization performance by electrochemical oxidation and electro-Fenton technologies

Electrochemical water treatment technologies are highly promising to achieve complete decolorization of dyebath effluents, as demonstrated by several studies reported in the literature. However, these works are focused on the treatment of one model pollutant and generalize the performances of the processes which are not transposable since they depend on the pollutant treated. Thus, in the present study, we evaluate, for the first time, the influence of different functional groups that modify the dye structure on the electrochemical process decolorization performance. The textile azo dyes Reactive Orange 16, Reactive Violet 4, Reactive Red 228, and Reactive Black 5 have been selected because they present the same molecular basis structure with different functional groups. The results demonstrate that the functional groups that reduce the nucleophilicity of the pollutant hinder the electrophilic attack of electrogenerated hydroxyl radical. Thereby, the overall decolorization efficiency is consequently reduced as well as the decolorization rate. Moreover, the presence of an additional chromophore azo bond in the molecule enhances the recalcitrant character of the azo dyes as pollutants. The formation of a larger and more stable conjugated π system increases the activation energy required for the electrophyilic attack of •OH, affecting the performance of electrochemical technologies on effluent decolorization.

Application of Advanced Oxidation Methods for Water Disinfection

Chlorination is the most used method in the world for drinking water disinfection. However, the identification of by-products potentially toxics generated by this method has encouraged the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered as suitable alternatives to replace the chlorination method. This review article gives a general overview about these treatment systems that can contribute to drinking water disinfection and it shows the efficiency of recently developed free-chlorine systems.

Electrochemical Oxidation of Oxalic Acid at Different Anode Materials: Applicability of Electroanalysis for Monitoring OA Degradation

The electrochemical oxidation (EO) of oxalic acid (OA) has been studied, in acidic media at Ti/PbO2, highly boron-doped diamond (BDD), Pt and graphite electrodes by applying 60 mAcm−2 of current density. Generally, EO is monitored by chromatography techniques; but the aim of this work is to show the applicability of electroanalysis for detection of OA concentration during its oxidation; by differential pulse voltammetry (DPV) using two different analytical procedures (by analytical curve and by successive addition standard). The results obtained by DPV analysis showed that OA was oxidized at several substrates to CO2 with different results, showing that the performances of the process dramatically depend on the anodic material. Higher removal efficiencies were obtained at Ti/PbO2, graphite and BDD anodes. Finally, DPV analyses were compared with classic titration method achieving a good fit, confidence intervals and limits. The results are described and discussed in the light of the existing literature.