María Isabel Díez-García

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.

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.

Study of Copper Ferrite as a Novel Photocathode for Water Reduction: Improving Its Photoactivity by Electrochemical Pretreatment

Studies on water-splitting p-type oxide electrodes based on nontoxic earth-abundant elements are scarce. Herein, the behavior of electrodes composed of CuFe2 O4 nanoparticles 30 nm in size is presented. The as-prepared CuFe2 O4 nanoporous electrodes exhibit small anodic photocurrents in 0.1 m NaOH. However, an electrochemical pretreatment consisting in the application of sufficiently positive potentials leads to p-type behavior with a photocurrent onset as high as 1.1 V versus the reversible hydrogen electrode, which is among the most positive values reported for an oxide absorbing visible light (band gap of 2.1 eV). This photocurrent is partly due to H2 evolution, but there are also signs of photoreduction of the material. Although the photocurrents are modest, these results point to the possibility of using CuFe2 O4 as a photocathode material in water-splitting devices. Furthermore, the strategy employed for the enhancement in the CuFe2 O4 photoactivity could be extended to other photocathode materials.

Investigating Water Splitting with CaFe2O4 Photocathodes by Electrochemical Impedance Spectroscopy.

Artificial photosynthesis constitutes one of the most promising alternatives for harvesting solar energy in the form of fuels, such as hydrogen. Among the different devices that could be developed to achieve efficient water photosplitting, tandem photoelectrochemical cells show more flexibility and offer high theoretical conversion efficiency. The development of these cells depends on finding efficient and stable photoanodes and, particularly, photocathodes, which requires having reliable information on the mechanism of charge transfer at the semiconductor/solution interface. In this context, this work deals with the preparation of thin film calcium ferrite electrodes and their photoelectrochemical characterization for hydrogen generation by means of electrochemical impedance spectroscopy (EIS). A fully theoretical model that includes elementary steps for electron transfer to the electrolyte and surface recombination with photogenerated holes is presented. The model also takes into account the complexity of the semiconductor/solution interface by including the capacitances of the space charge region, the surface states and the Helmholtz layer (as a constant phase element). After illustrating the predicted Nyquist plots in a general manner, the experimental results for calcium ferrite electrodes at different applied potentials and under different illumination intensities are fitted to the model. The excellent agreement between the model and the experimental results is illustrated by the simultaneous fit of both Nyquist and Bode plots. The concordance between both theory and experiments allows us to conclude that a direct transfer of electrons from the conduction band to water prevails for hydrogen photogeneration on calcium ferrite electrodes and that most of the carrier recombination occurs in the material bulk. In more general vein, this study illustrates how the use of EIS may provide important clues about the behavior of photoelectrodes and the main strategies for their improvement.

Metal Doping to Enhance the Photoelectrochemical Behavior of LaFeO3 Photocathodes

The development of tandem devices for water photosplitting requires the preparation of photocathodic materials based on earth-abundant elements that show long-term stability in aqueous electrolytes. Ternary metal oxides seem to be a viable option, among which perovskites stand out. In this context, transparent and compact LaFeO3 thin-film electrodes have been prepared by a sol-gel process, both undoped and doped with metals (M) such as Mg or Zn. Pristine electrodes support the development of cathodic photocurrents in 0.1 m NaOH aqueous solutions, particularly in the presence of oxygen, with an onset potential as high as 1.4 V versus the reversible hydrogen electrode. Doping with Mg or Zn leads to an important enhancement of the photocurrent, which peaks for a stoichiometry of LaFe0.95 M0.05 O3 with a sixfold enhancement with respect to the pristine material. Such an improvement is attributed to an increase in both the density and mobility of the majority carriers, although a contribution of surface passivation cannot be excluded.

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.