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The hydrogen reversible reaction (HRR) with ultra-low concentrations of platinum sites supported on a gold substrate is studied with decreasing amounts of active sites (estimate coverage range from 0.006 to 10− 5) at a rotating electrode in a 0.5 M H2SO4 solution. These particular experimental conditions allow the voltammetric study of the HRR without diffusion limitation in the whole range of potential. In the absence of a more precise determination of the amount of platinum surface sites, a method is given to compare results obtained from distinct experimental runs. Once eliminated the contribution of gold to the current recorded, it becomes possible to normalize the currents in the entire range of platinum coverage. It shows that below 0.2 V, the normalized HER and the HOR currents are linearly connected to the amount of active sites. At higher potentials the normalized currents indicate a systematic decrease of the efficiency of the active sites for HOR that deviates from linearity when their surface concentration decreases. Around the reversible potential, the voltammetric profiles obey to the Butler-Volmer formalism. The conditions of its applicability are discussed. The simulation of the experimental current allows the determination of the partial oxidation and reduction currents. The simulated reduction current is then compared to the HER current recorded in a solution without dissolved hydrogen and saturated with argon. The close fit of the two responses gives evidence for the possibility to have access to HER kinetic data free of diffusion. Finally a comparison is made between results obtained at ultra-low content of platinum active sites with pure platinum as well as for an intermediate coverage of gold with platinum.

In this paper, we present a new Acid-Base Electrochemical Flow Battery (ABEFB). This system is composed of acidic and alkaline solutions, both with a high supporting electrolyte concentration. These solutions are separated by a proton exchange membrane, using hydrogen as both a reactant and a product. Under this configuration, neutralization energy is used as electromotive force. Thus, in the charging process, hydrogen is oxidized to form hydronium ions (hydrogen oxidation reaction –HOR-) (positive electrode) that acidifies positive electrolyte or posilyte, while hydrogen is formed from water (hydrogen evolution reaction –HER-) (negative electrode) that basifies negative electrolyte or negalyte. On the other hand, during the discharging process, both electrolytes are neutralized through hydrogen oxidation and hydrogen evolution reactions. A platinised titanium electrode is chosen for HER and a platinum-catalysed gas diffusion electrode is used for HOR. This proof of concept has been verified for several charge capacities obtaining a maximum power density of 20 mW cm−2 at 49 mA cm−2. In this sense, faradaic efficiency close to 95% and energy efficiency of 55% are also obtained. Finally, the reuse of produced hydrogen is an interesting aspect to be considered.

Microbial electrochemical technologies (METs) constitute the core of a number of emerging technologies with a high potential for treating urban wastewater due to a fascinating reaction mechanism—the electron transfer between bacteria and electrodes to transform metabolism into electrical current. In the current work, we focus on the model electroactive microorganism Geobacter sulfurreducens to explore both the design of new start-up procedures and electrochemical operations. Our chemostat-grown plug and play cells, were able to reduce the start-up period by 20-fold while enhancing chemical oxygen demand (COD) removal by more than 6-fold during this period. Moreover, a filter-press based bioreactor was successfully tested for both acetate-supplemented synthetic wastewater and real urban wastewater. This proof-of-concept pre-pilot treatment included a microbial electrolysis cell (MEC) followed in time by a microbial fuel cell (MFC) to finally generate electrical current of ca. 20 A·m−2 with a power of 10 W·m−2 while removing 42 g COD day−1·m−2. The effective removal of acetate suggests a potential use of this modular technology for treating acetogenic wastewater where Geobacter sulfurreducens outcompetes other organisms.

One of the typical problems addressed in electrochemical textbooks is how to define the theoretical kinetic law of an electrochemical reaction and how to propose a plausible mechanism for this reaction from its kinetic parameters, usually the Tafel slope and reaction orders.

In this work, electrodialysis has been proved to be a suitable technique for decreasing the conductivity of a real wastewater from an almond industry, which has been previously treated by electrocoagulation (EC) and electrooxidation (EO). A seven-cell electrodialyzer, with total active membrane area of 1400 cm2, was employed and several parameters, as the limiting current density, were determined. A method for measuring voltage across the membranes was developed, in order to control membrane fouling. The method consisted of capillaries inserted into the solution compartments and connected to a high impedance voltmeter. A study of the reuse of the concentrate solution was made, and it was stated that it can be concentrated 10 times. The treatment of the wastewater was performed at different voltages (7–16 V) to reach values of conductivity of the diluate of 0.5 mS cm−1. After that, the scaling up to a pre-industrial scale was performed by using a 70-cell electrodialyzer, with total active membrane area of 3.5 m2. The process was performed by applying voltages of 20–70 V and a final conductivity of the diluate of 0.5 mS cm−1 was achieved. The electric energy consumption was calculated in every case.

A pesar del amplio abanico de aplicaciones que posee la electroquímica, con importantes repercusiones en muchos aspectos de la vida cotidiana, los egresados de química de las universidades españolas poseen en general un notable desconocimiento de esta materia. Con objeto de hacer más atractivo el aprendizaje de esta parte de la química, al tiempo que se revelan algunas de sus aplicaciones menos conocidas, se han preparado nuevos materiales didácticos. En ellos se describen de manera divulgativa algunas de las aplicaciones más importantes de la electroquímica, como son las baterías, síntesis de aluminio, o su uso en biosensores. Los nuevos materiales se han suministrado al alumnado del primer curso del grado de química de la Universidad de Alicante y se ha pedido su opinión a través de una encuesta. En general la recepción ha sido buena, aunque la respuesta de los estudiantes ha sido algo escasa. Para dar mayor difusión, se está creando una página web con estos mismos contenidos. Esta página web se ha puesto a disposición de los alumnos de la asignatura Electroquímica de 4º curso de la licenciatura (plan a extinguir) de Química y de nuevo se pedirá su opinión a través de un formulario web.

The use of a solid polymeric electrolyte, spe, is not commonly found in organic electrosynthesis despite its inherent advantages such as the possible elimination of the electrolyte entailing simpler purification processes, a smaller sized reactor and lower energetic costs. In order to test if it were possible to use a spe in industrial organic electrosynthesis, we studied the synthesis of 1-phenylethanol through the electrochemical hydrogenation of acetophenone using Pd/C 30 wt% with different loadings as cathode and a hydrogen gas diffusion anode. A Polymer Electrolyte Membrane Electrochemical Reactor, PEMER, with a fuel cell structure was chosen to carry out electrochemical reduction with a view to simplifying an industrial scale-up of the electrochemical process. We studied the influence of current density and cathode catalyst loading on this electroorganic synthesis. Selectivity for 1-phenylethanol was around 90% with only ethylbenzene and hydrogen detected as by-products.

In this paper we have studied how the deposition of platinum adatoms at gold electrode surface in undetectable amount by observation of the gold electrode CV profile may put in evidence the first stage of the appearance of a catalytic activity for a material initially inactive. In this respect, we will show that the electrochemical hydrogen oxidation reaction (HOR) is an extremely sensitive surface probe for detection of very small amount of surface active sites such as platinum adatoms below 10−4 ML. The activity of the site is revealed by its ability to oxidize hydrogen from the solution in contrast with the gold substrate. The present results open new perspectives for improving the description of the hydrogen redox reaction in particular by a strong decrease of diffusion limitation. It results a possibility to put in evidence for the HOR the existence of two polarization regions as a consequence of two consecutive steps. At low overpotential, the electronic transfer is the slow step, whereas for higher overpotential values the hydrogen adsorption on the active sites becomes the rate limiting step as a consequence of the competitive adsorption with the solution components.

The pre-pilot scale synthesis of 1-phenylethanol was carried out by the cathodic hydrogenation of acetophenone in a 100 cm2 (geometric area) Polymer Electrolyte Membrane Electrochemical Reactor. The cathode was a Pd/C electrode. Hydrogen oxidation on a gas diffusion electrode was chosen as anodic reaction in order to take advantage of the hydrogen evolved during the reduction. This hydrogen oxidation provides the protons needed for the synthesis. The synthesis performed with only a solid polymer electrolyte, spe, has lower fractional conversion although a higher selectivity than that carried out using a support–electrolyte–solvent together with a spe. However, the difference between these two cases is rather small and since the work-up and purification of the final product are much easier when only a spe is used, this last process was chosen for the pre-pilot electrochemical synthesis of 1-phenylethanol.

Oxidation (HPOR) and reduction (HPRR) reactions of hydrogen peroxide were studied on platinum single crystalline surfaces. Experimental curves were fitted to a simple model in which the whole process is described by the sum of two independent, mass controlled reactions. It is shown that stepped surfaces are more catalytic than basal planes for both HPOR and HPRR reactions. On the contrary, on oxide covered surfaces, those having large {111} terraces are better electrocatalysts for HPRR, but worse for HPOR. These results shed light concerning H2O2 reactivity on platinum surfaces and may help to unveil oxygen reduction reaction mechanism.

The electrochemical reactivity of catechol-derived adlayers is reported at platinum (Pt) single-crystal electrodes. Pt(111) and stepped vicinal surfaces are used as model surfaces possessing well-ordered nanometer-sized Pt(111) terraces ranging from 0.4 to 12 nm. The electrochemical experiments were designed to probe how the control of monatomic step-density and of atomic-level step structure can be used to modulate molecule–molecule interactions during self-assembly of aromatic-derived organic monolayers at metallic single-crystal electrode surfaces. A hard sphere model of surfaces and a simplified band formation model are used as a theoretical framework for interpretation of experimental results. The experimental results reveal (i) that supramolecular electrochemical effects may be confined, propagated, or modulated by the choice of atomic level crystallographic features (i.e.monatomic steps), deliberately introduced at metallic substrate surfaces, suggesting (ii) that substrate-defect engineering may be used to tune the macroscopic electronic properties of aromatic molecular adlayers and of smaller molecular aggregates.

In this work carbon supported Pd nanoparticles were prepared and used as electrocatalysts for formic acid electrooxidation fuel cells. The influence of some relevant parameters such as the nominal Pt loading, the Nafion/total solids ratio as well as the Pd loading towards formic acid electrooxidation was evaluated using gold supported catalytic layer electrodes which were prepared using a similar methodology to that employed in the preparation of conventional catalyst coated membranes (CCM). The results obtained show that, for constant Pd loading, the nominal Pd loading and the Nafion percentage on the catalytic layer do not play an important role on the resulting electrocatalytic properties. The main parameter affecting the electrocatalytic activity of the electrodes seems to be the Pd loading, although the resulting activity is not directly proportional to the increased Pd loading. Thus, whereas the Pd loading is multiplied by a factor of 10, the activity is only twice which evidences an important decrease in the Pd utilization. In fact, the results obtained suggest the active layer is the outer one being clearly independent of the catalytic layer thickness. Finally, catalyst coated membranes with Pd catalyst loadings of 0.1, 0.5 and 1.2 mg cm-2 were also tested in a breathing direct formic acid fuel cell.

La electroquímica es una parte importante de la química, incluida en la mayoría de los temarios de diversas ciencias experimentales. Las reacciones químicas con transferencia de electrones aparecen en numerosas situaciones de la vida cotidiana y constituyen un aspecto muy importante en las reacciones biológicas. A pesar de su importancia, la electroquímica suele ser percibida por los estudiantes con dificultad pues incluye conceptos algo abstractos, como el de potencial eléctrico, que combinados con los propios conceptos de química, tienden a desconcertar al alumno. El objetivo del presente trabajo de investigación docente es la elaboración de un portafolio de ejemplos en los que aparece la electroquímica en el ámbito cotidiano. El uso de baterías y acumuladores es ampliamente conocido. Sin embargo, es menos conocido el papel de la electroquímica en síntesis de gran importancia industrial como la del cloro, el aluminio o el nylon. La electroquímica aparece también entre los principios de funcionamiento de diversos biosensores, como los sistemas de control de alcoholemia o glucosa en sangre. Los ejemplos seleccionados servirán para introducir diversos aspectos de la electroquímica, pretendiendo despertar el interés por esta parte de la ciencia.

Food industries such as almond industry generate large volumes of wastewater in their processes and common techniques are not always efficient for treating this kind of effluents. In this work, the feasibility of a treatment for pollutants removal of a real industrial wastewater by electrochemical oxidation s studied at laboratory scale and then scaled-up to pre-industrial scale. The first stage of the work was performed at laboratory scale, using a 63 cm2 cell, where different anodes (Ti/Pt, and DSA anodes (Ti/RuO2 and Ti/IrO2)) and the optimal experimental conditions (pH, current density, temperature and [Cl-]) were studied and established. By using a DSA-Cl2 anode (Ti/RuO2), pH 9, j = 50 mA cm-2, [Cl-] = 2000 mg L-1 and room temperature, chemical oxygen demand (COD) was removed up to 75% and results show that electrooxidation can remove organic pollutants. In the second stage the scaling-up of the process from laboratory to pre-industrial scale was performed, by using a 3300cm2 cell. The electrochemical reactor was finally powered by a photovoltaic generator directly connected, in order to operate by using a renewable energy and a COD elimination of 80% was achieved.

En esta tesis doctoral se han estudiado las diferentes opciones que presenta la síntesis electroquímica como vía de aprovechamiento del CO2, gas que contribuye en gran medida al efecto invernadero. 1. La reducción electroquímica de CO2 empleando electrodos de difusión de gas, que permite la obtención de gas de síntesis en proporciones H 2/CO controladas. 2. Distintas reacciones de carboxilación electroquímica, muy útiles para la obtención de compuestos orgánicos que contengan grupos carboxílicos. Estas reacciones se han llevado a cabo empleando como sustrato halopiridinas, iminas cíclicas y acetonitrilo. Además, en algunos casos se han aprovechado las propiedades electrocatalíticas de los electrodos de plata para mejorar el rendimiento del producto carboxilado. 3. La reducción electroquímica de ácidos carboxílicos derivados de isoquinolina y quinolina, que en función de las condiciones pueden dar lugar a un proceso o bien de descarboxilación reductiva o bien de hidroxilación electroquímica., It has been studied in this thesis the different options that the electrochemical synthesis provides as a way to use the CO2, gas that mainly contributes to the greenhouse effect. 1. The electrochemical reduction of CO2 using gas diffusion electrodes, which allows the production of syngas in a controllable H 2/CO ratio. 2. Different electrochemical carboxylation reactions, very useful for the production of organic compounds that contain carboxylic groups. Theses reactions have been carried out using halopyridines, cyclic imines and acetonitrile as substrates. Besides, the electrocatalytic properties of silver electrodes have been used in some cases to improve the carboxylated product yield. 3. The electrochemical reduction of isoquinoline and quinoline carboxylic acid derivatives, which can produce either a reductive decarboxylation reaction or a electrochemical hydroxylation reaction depending on the experimental conditions.

A new electrochemical redox probe has been investigated in order to characterize the local production of radicals during the cavitation events. The results have been compared with those obtained with Fe(CN)6 3-/Fe(CN)6 4- (electrochemical probe for local mechanical effects) and classical chemical methods such as iodide and Fricke dosimeters (chemical probes for global effects).

Numerical simulations have been carried out in order to characterize the ultrasonic field propagation and to obtain the spatial distribution of the mechanical effect derived from it. The results have been compared with those obtained with different classical physical methods (calorimetry, aluminium foil erosion, thermal probes) and have given useful information about the influence of the presence of probes and auxiliary tools in the ultrasonic field. All these information have been used for the development of the Part II of this work: analysis of chemical effects, providing an accurate picture of the reaction environment in the sonoreactor used (20 kHz, 100 W supplied by Undatim) for further uses in sonoelectrochemical studies.

Se puede dividir la presente memoria en dos grandes partes interconectadas entre sí y cuyo fin será la obtención de un diseño de reactor más eficiente, que los fabricados hasta el momento en la Universidad de Alicante, obtenido a través de diversos métodos de optimización que evitarán la construcción de muchos prototipos de prueba disminuyendo significativamente los recursos económicos que se deberán destinar para alcanzar este objetivo. Por otro lado, a lo largo de la presente memoria se irán empleando diversas técnicas y herramientas que serán puestas a punto para desarrollar la tarea de conseguir una optimización más rápida, eficiente y barata de esta clase de reactores.

The influence of the ultrasonic frequency on the electrocrystallisation of lead dioxide on glassy carbon electrodes was studied in 1 mol dm−3 HNO3 + 0.1 mol dm−3 Pb(NO3)2 using chronoamperometry and numerical approximations of the current transients obtained. The effects of the ultrasound frequency have been compared with the effects produced by other operational variables such as electrode potential.