Nuevos materiales didácticos para descubrir los aspectos más cotidianos de la Electroquímica

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.

Un nuevo enfoque didáctico para acercar la Electroquímica al alumnado a través de experiencias cotidianas

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.

Congreso online como herramienta docente para estudiantes de tercer ciclo en Electroquímica

Los congresos científicos son una buena herramienta para que los estudiantes de tercer ciclo puedan ampliar sus conocimientos. Sin embargo, las intervenciones donde los estudiantes plantean dudas o preguntas son prácticamente nulas. Con el objetivo de fomentar la participación de los estudiantes en los congresos científicos, la nueva red continua con el trabajo anteriormente realizado, llevando a cabo la II edición del Congreso online de estudiantes dentro del programa interuniversitario “Electroquímica. Ciencia y Tecnología”. La red busca concienciar acerca de la importancia que para un investigador tiene un congreso científico y a su vez, incrementar y mejorar su participación. Para ello, se utiliza un formato más atractivo que en la edición anterior, que mejora el entorno de trabajo y favorece la interacción entre los estudiantes. Asimismo, se emplean estrategias de comunicación más desarrolladas para hacer crecer el número de participantes. Finalmente, se establecerán diferentes parámetros para evaluar la actividad durante el congreso y se entregarán premios para motivar la participación.

Evidence of Local pH Changes during Ethanol Oxidation at Pt Electrodes in Alkaline Media

Local changes of the interfacial pH can significantly affect the rate and mechanism during the course of an electrodic reaction. For instance, different pH values will have a significant effect on the equilibrium properties of both solution and surface species, altering the reactions kinetics. Ethanol oxidation at platinum electrodes in alkaline media involves the fast consumption of OH− species that will change the local pH at the electrode surface, decreasing the reaction rate. In this study, the local pH change during ethanol oxidation in alkaline media is accomplished by using rotating ring-disc electrode (RRDE) experiments. The current at the ring when polarized at the onset of hydrogen evolution serves as a measure of the local pH in the vicinity of the electrode. The results show that the current at the ring at 0.1 V (vs. RHE) becomes more negative during ethanol oxidation, owing to a change in the equilibrium potential of the hydrogen evolution reaction caused by a change in the local pH.

Electrochemical Characterization of Shape-Controlled Pt Nanoparticles in Different Supporting Electrolytes

The voltammetric profile of preferentially shaped platinum nanoparticles has been used to analyze the different sites present on the surface. For the first time, this analysis has been made in NaOH solutions and revisited in sulfuric and perchloric acid media. The comparison with the voltammetric profiles of the model surfaces, that is, single-crystal electrodes, allows assigning the different signals appearing in the voltammograms of the nanoparticle to specific sites on the surface. A good correlation between the shape of the nanoparticle determined by TEM and the voltammetric profile is obtained. For the nanoparticles characterized in alkaline media, the adsorbed species on the surface have been characterized, and three major regions can be identified. Below 0.2 V, the major contribution is due to hydrogen adsorption, whereas above 0.6 V, adsorbed OH is the main species on the surface. Between those values, the signals are due to the competitive adsorption/desorption process of OH/H. New criteria for determining the active area in NaOH solutions has been proposed. In this medium, the total charge density measured between 0.06 and 0.90 V stands for 390 μC cm–2. The areas measured are in perfect agreement with those measured in acid media. Once the nanoparticles have been characterized, the behavior of the nanoparticles toward CO oxidation is analyzed and compared with that observed for single-crystal electrodes.

Oxidation of Ethanol and Its Derivatives on Well Defined Pt Single Crystal Electrodes Vicinal to Pt(111): A Comparative Study

The oxidation of ethanol (EtOH) at Pt(111) electrodes is dominated by the 4e path leading to acetic acid. The inclusion of surface defects such as those present on stepped surfaces leads to an increase of the reactivity towards the most desirable 12e path leading to CO2 as final product. This path is also favored when the methyl group is more oxidized, as in the case of ethylene glycol (EG) that spontaneously decomposes to CO on Pt(111) electrodes, thus showing a more effective breaking of the C-C bond. Some trends in reactivity can be envisaged when other derivative molecules are compared at well-ordered electrodes. This strategy was used in the past, but the improvement in the electrode pretreatment and the overall information available on the subject suggest that relevant information is still missing.

On the behavior of the Pt(1 0 0) and vicinal surfaces in alkaline media

We address in this paper a voltammetric study of the charge transfer processes characteristic of Pt(1 0 0) and vicinal surfaces in alkaline media. The electrochemical behavior of a series of stepped surfaces of the type Pt(S)[n(1 0 0) × (1 1 1)] has been characterized using cyclic voltammetry at different pHs, charge displacement measurements and FTIR experiments for adsorbed CO. The results from these techniques allow assigning the different peaks appearing in the voltammogram to hydrogen and/or OH adsorption on the different sites of these surfaces, namely, terrace and step sites. Additionally, the potential of zero total charge (pztc) of the electrodes was determined. The resulting pztc values shift to more negative values when the step density increases on the surface up to n = 5. FTIR spectroscopy experiments have been used to monitor the adsorption of CO on the different surfaces as well as the consequent CO oxidation, accompanying a positive potential sweep. The oxidation of adsorbed CO on (1 0 0) terraces is catalyzed by the presence of the (1 1 1) steps. The FTIR spectra revealed that CO is mostly bonded in bridge configuration at low potentials interconverting to on-top when the electrode potential is increased.

Elemental Anisotropic Growth and Atomic-Scale Structure of Shape-Controlled Octahedral Pt–Ni–Co Alloy Nanocatalysts

Multimetallic shape-controlled nanoparticles offer great opportunities to tune the activity, selectivity, and stability of electrocatalytic surface reactions. However, in many cases, our synthetic control over particle size, composition, and shape is limited requiring trial and error. Deeper atomic-scale insight in the particle formation process would enable more rational syntheses. Here we exemplify this using a family of trimetallic PtNiCo nanooctahedra obtained via a low-temperature, surfactant-free solvothermal synthesis. We analyze the competition between Ni and Co precursors under coreduction “one-step” conditions when the Ni reduction rates prevailed. To tune the Co reduction rate and final content, we develop a “two-step” route and track the evolution of the composition and morphology of the particles at the atomic scale. To achieve this, scanning transmission electron microscopy and energy dispersive X-ray elemental mapping techniques are used. We provide evidence of a heterogeneous element distribution caused by element-specific anisotropic growth and create octahedral nanoparticles with tailored atomic composition like Pt1.5M, PtM, and PtM1.5 (M = Ni + Co). These trimetallic electrocatalysts have been tested toward the oxygen reduction reaction (ORR), showing a greatly enhanced mass activity related to commercial Pt/C and less activity loss than binary PtNi and PtCo after 4000 potential cycles.

Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering

We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500–1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.