V. Sáez

Current topics on sonoelectrochemistry

Sonoelectrochemistry is undergoing a reemerging activity in the last years with an increasing number of papers appearing in a wide range of peer review journals. Applied studies which cover environmental treatments, synthesis or characterization of nanostructures, polymeric materials synthesis, analytical procedures, films preparations, membrane preparations among other interesting applications have been reviewed. The revised fundamental analyses trying to elucidate the mechanism of the interactions between the ultrasound and electrical fields, are focused on test electrochemical processes, on the use of unconventional solvents and combination with other techniques. After the review of the achievements and faults of sonoelectrochemistry, future research lines are suggested.

Simulation of the spatial distribution of the acoustic pressure in sonochemical reactors with numerical methods: a review

Numerical methods for the calculation of the acoustic field inside sonoreactors have rapidly emerged in the last 15 years. This paper summarizes some of the most important works on this topic presented in the past, along with the diverse numerical works that have been published since then, reviewing the state of the art from a qualitative point of view. In this sense, we illustrate and discuss some of the models recently developed by the scientific community to deal with some of the complex events that take place in a sonochemical reactor such as the vibration of the reactor walls and the nonlinear phenomena inherent to the presence of ultrasonic cavitation. In addition, we point out some of the upcoming challenges that must be addressed in order to develop a reliable tool for the proper designing of efficient sonoreactors and the scale-up of sonochemical processes.

FEM simulation of a sono-reactor accounting for vibrations of the boundaries

The chemical effects of acoustic cavitation are obtained in sono-reactors built-up from a vessel and an ultrasonic source. In this paper, simulations of an existing sono-reactor are carried out, using a linear acoustics model, accounting for the vibrations of the solid walls. The available frequency range of the generator (19-21 kHz) is systematically scanned. Global quantities are plotted as a function of frequency in order to obtain response curves, exhibiting several resonance peaks. In absence of the precise knowledge of the bubbles size distribution and spatial location, the attenuation coefficient of the wave is taken as a variable, but spatially uniform parameter, and its influence is studied. The concepts of acoustic energy, intensity, active power, and source impedance are recalled, along with the general balance equation for acoustic energy, which is used as a convergence check of the simulations. It is shown that the interface between the liquid and the solid walls cannot be correctly represented by the simple approximations of either infinitely soft, or infinitely hard boundaries. Moreover, the liquid-solid coupling allows the cooling jacket to receive a noticeable part of the input power, although it is not in direct contact with the sonotrode. It may therefore undergo cavitation and this feature opens the perspective to design sono-reactors which avoid direct contact between the working liquid and the sonotrode. Besides, the possibility to shift the main pressure antinode far from the sonotrode area by exciting a resonance of the system is examined.

Electrochemical degradation of perchloroethylene in aqueous media: an approach to different strategies.

An approaching study to the electrochemical degradation of perchloroethylene (PCE) in water has been carried out using controlled current density degradation electrolyses. The different electrochemical strategies to degrade perchloroethylene in aqueous media (i.e. cathodic, anodic and dual treatments) have been checked using divided and undivided configurations. The influence of the initial concentration, pH and current density on the general behavior of the system has been studied, and special attention was paid to the nature of the byproducts formed and to the analysis of the closed mass balance at the end of the reaction. Results from several analytical techniques have been compared. Undivided configuration provides the best results in these experimental conditions, with degradation percentages higher than 50% and with only 6% of the initial perchloroethylene concentration remaining in the system.

Sonoelectrochemical treatment of water polluted with trichloroacetic acid: From sonovoltammetry to pre-pilot plant scale

The sonoelectrochemical treatment of aqueous solutions of trichloroacetic acid (TCAA) has been scaled-up from the voltammetric analysis to pre-pilot stage. The degradation in absence of ultrasound field has yield to a poor performance which has been improved in presence of ultrasound. The sonovoltametry study has provided the range of potentials and/or current densities to be used with the lowest current efficiency penalty. Sonoelectrolyses at batch scale (carried out with a horn-transducer 24 kHz positioned at about 3 cm from the surface of the electrode) achieved little improvement in the degradation. However, when a specifically designed sonoelectrochemical reactor (not optimized) was used during the scale-up, the presence of ultrasound field provided better results (fractional conversion 97%, degradation efficiency 26%, selectivity 0.92 and current efficiency 8%) at lower ultrasonic intensities and volumetric flow.

Lead dioxide film sonoelectrodeposition in acidic media: Preparation and performance of stable practical anodes.

Practical lead dioxide anodes have been obtained by electrodeposition on glassy carbon and titanium substrates in the presence and in the absence of an ultrasound field. The films obtained by mechanical agitation on glassy carbon are strongly improved when the electrodeposition process is carried out with the ultrasound field, providing adherent deposits free from nodules and stress, but with pores appearing occasionally. These enhanced properties were not achieved by mechanical conditions, even when optimization of temperature, current density, additives and geometrical aspects was attempted. The best practical anodes were obtained by sonoelectrodeposition using specially treated titanium as substrate, providing comparable behavior to commercial electrodes.

Sonochemical degradation of perchloroethylene: the influence of ultrasonic variables, and the identification of products.

Sonochemistry is a technique that offers promise for pollutant degradation, but earlier studies on various chlorinated substrates do not give a definitive view of the effectiveness of this methodology. We now report a thorough study of ultrasonic operational variables upon perchloroethylene (PCE) degradation in water (variables include ultrasonic frequency, power and system geometry as well as substrate concentration) and we attempt to close the mass balance where feasible. We obtained fractional conversions of >97% showing very effective loss of pollutant starting material, and give mechanistic proposals for the reaction pathway based on cavitational phenomena inducing pyrolytic and free radical processes. We note major products of Cl(-) and CO(2)/CO, and also trichloroethylene (TCE) and dichloroethylene (DCE) at ppm concentrations as reported earlier. The formation at very low (ppb) concentration of small halocompounds (CHCl(3), CCl(4)) and also of higher-mass species, such as pentachloropropene, hexachloroethane, is noteworthy. But of particular importance in our work is the discovery of significant quantities of chloroacetate derivatives at ppm concentrations. Although these compounds have been described as by-products with other techniques such as radiolysis or photochemistry, this is the first time that these products have been identified in the sonochemical treatment of PCE; this allows a much more effective account of the mass balance and may explain earlier inconsistencies. This reaction system is now better identified, but a corollary is that, because these haloacetates are themselves species of some toxicity, the use of ultrasound here may not sufficiently diminish wastewater toxicity.

Sonopotential: a new concept in electrochemistry.

The application of ultrasound to a solution in contact with a semiconductor working electrode leads to a change in its open circuit potential, that is, to the appearance of a sonopotential sensitive to both ultrasonic power and solution composition.

Hybrid Sonochemical Treatments of Wastewater: Sonophotochemical and Sonoelectrochemical Approaches. Part II: Sonophotocatalytic and Sonoelectrochemical Degradation of Organic Pollutants

Sonochemical oxidation is one of the advanced oxidation techniques that are widely used to decompose various organic contaminants in aqueous environment. Recent studies have suggested that the use of hybrid techniques is more effective compared to individual techniques for the decomposition of organic contaminants. The combination of more than one oxidation technique overcomes the disadvantages of individual techniques. This chapter provides a very detailed analysis of the sonochemical, sonophotocatalytic, and sonoelectrochemical degradation of various organic pollutants in aqueous environment. In addition to providing experimental data including kinetic information on the degradation reactions, specific examples have been analyzed in terms of their reaction mechanisms.

Electrochemical degradation of trichloroacetic acid in aqueous media: influence of the electrode material

The electrochemical degradation of trichloroacetic acid (TCAA) in water has been analysed through voltammetric studies with a rotating disc electrode and controlled-potential bulk electrolyses. The influence of the mass-transport conditions and initial concentration of TCAA for titanium, stainless steel and carbon electrodes has been studied. It is shown that the electrochemical reduction of TCAA takes place prior to the massive hydrogen evolution in the potential window for all electrode materials studied. The current efficiency is high (>18%) compared with those normally reported in the literature, and the fractional conversion is above 50% for all the electrodes studied. Only dichloroacetic acid (DCAA) and chloride anions were routinely detected as reduction products for any of the electrodes, and reasonable values of mass balance error were obtained. Of the three materials studied, the titanium cathode gave the best results.