Electrochemical Performance of Hierarchical Porous Carbon Materials Obtained from the Infiltration of Lignin into Zeolite Templates

Hierarchical porous carbon materials prepared by the direct carbonization of lignin/zeolite mixtures and the subsequent basic etching of the inorganic template have been electrochemically characterized in acidic media. These lignin-based templated carbons have interesting surface chemistry features, such as a variety of surface oxygen groups and also pyridone and pyridinic groups, which results in a high capacitance enhancement compared to petroleum-pitch-based carbons obtained by the same procedure. Furthermore, they are easily electro-oxidized in a sulfuric acid electrolyte under positive polarization to produce a large amount of surface oxygen groups that boosts the pseudocapacitance. The lignin-based templated carbons showed a specific capacitance as high as 250 F g−1 at 50 mA g−1, with a capacitance retention of 50 % and volumetric capacitance of 75 F cm−3 at current densities higher than 20 A g−1 thanks to their suitable porous texture. These results indicate the potential use of inexpensive biomass byproducts, such as lignin, as carbon precursors in the production of hierarchical carbon materials for electrodes in electrochemical capacitors.

Effects of Ultrasound Irradiation on the Synthesis of Metal Oxide Nanostructures

High intensity ultrasound can be used for the production of novel nanomaterials, including metal oxides. According to previous works in this field, the most notable effects are consequence of acoustic cavitation. In this context, we have studied the preparation of different materials in the presence of ultrasound, including N-doped TiO2 nanopowder, NiTiO3 nanorods and MnOx thin films. Ultrasound did not show a significant effect in all the cases. Exclusively for NiTiO3 nanorods a reduction of the final particle size occurs upon ultrasonic irradiation. From these results, it can be concluded that the ultrasound irradiation does not always play a key role during the synthesis of metal oxides. The effects seem to be particularly relevant in those cases where mass transport is highly hindered and in those procedures that require the rupture of nanoparticle aggregates to obtain a homogenous dispersion.

Production of methanol from CO2 electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution

In this study, we examine the performance of Cu2O and Cu2O/ZnO surfaces in a filter-press electrochemical cell for the continuous electroreduction of CO2 into methanol. The electrodes are prepared by airbrushing the metal particles onto a porous carbon paper and then are electrochemically characterized by cyclic voltammetry analyses. Particular emphasis is placed on evaluating and comparing the methanol production and Faradaic efficiencies at different loadings of Cu2O particles (0.5, 1 and 1.8 mg cm−2), Cu2O/ZnO weight ratios (1:0.5, 1:1 and 1:2) and electrolyte flow rates (1, 2 and 3 ml min−1 cm−2). The electrodes including ZnO in their catalytic surface were stable after 5 h, in contrast with Cu2O-deposited carbon papers that present strong deactivation with time. The maximum methanol formation rate and Faradaic efficiency for Cu2O/ZnO (1:1)-based electrodes, at an applied potential of −1.3 V vs. Ag/AgCl, were r = 3.17 × 10−5 mol m−2 s−1 and FE = 17.7 %, respectively. Consequently, the use of Cu2O–ZnO mixtures may be of application for the continuous electrochemical formation of methanol, although further research is still required in order to develop highly active, selective and stable catalysts the electroreduction of CO2 to methanol.

Generation of nitrogen functionalities on activated carbons by amidation reactions and Hofmann rearrangement: Chemical and electrochemical characterization

Nitrogen functionalization of a highly microporous activated carbon (BET surface area higher than 3000 m2/g) has been achieved using the following sequence of treatments: (i) chemical oxidation using concentrated nitric acid, (ii) amidation by acyl chloride substitution with NH4NO3 and (iii) amination by Hoffman rearrangement. This reaction pathway yielded amide and amine functional groups, and a total nitrogen content higher than 3 at.%. It is achieved producing only a small decrease (20%) of the starting microporosity, being most of it related to the initial wet oxidation of the activated carbon. Remarkably, nitrogen aromatic rings were also formed as a consequence of secondary cyclation reactions. The controlled step-by-step modification of the surface chemistry allowed to assess the influence of individual nitrogen surface groups in the electrochemical performance in 1 M H2SO4 of the carbon materials. The largest gravimetric capacitance was registered for the pristine activated carbon due to its largest apparent surface area. The nitrogen-containing activated carbons showed the highest surface capacitances. Interestingly, the amidated activated carbon showed the superior capacitance retention due to the presence of functional groups (such as lactams, imides and pyrroles) that enhance electrical conductivity through their electron-donating properties, showing a capacitance of 83 F/g at 50 A/g.

Spectroelectrochemical Study of the Photoinduced Catalytic Formation of 4,4′-Dimercaptoazobenzene from 4-Aminobenzenethiol Adsorbed on Nanostructured Copper

Surface-enhanced raman scattering (SERS) spectra of self-assembled monolayers of 4-aminobenzenethiol (4-ABT) on copper (Cu) and silver (Ag) surfaces decorated with Cu and Ag nanostructures, respectively, have been obtained with lasers at 532, 632.8, 785, and 1064 nm. Density functional theory (DFT) has been used to obtain calculated vibrational frequencies of the 4-ABT and 4,4′-dimercaptoazobenzene (4,4′-DMAB) molecules adsorbed on model Cu surfaces. The features of the SERS spectra depend on the electrode potential and the type and power density of the laser. SERS spectra showed the formation of the 4,4′-DMAB on the nanostructured Cu surface independently of the laser employed. For the sake of comparison SERS spectra of a self-assembled monolayer of the 4-ABT on Ag surfaces decorated with Ag nanostructures have been also obtained with the same four lasers. When using the 532 and 632.8 nm lasers, the 4,4′-DMAB is formed on Cu surface at electrode potentials as low as −1.0 V (AgCl/Ag) showing a different behavior with respect to Ag (and others metals such as Au and Pt). On the other hand, the surface-enhanced infrared reflection absorption (SEIRA) spectra showed that in the absence of the laser excitation the 4,4′-DMAB is not produced from the adsorbed 4-ABT on nanostructured Cu in the whole range of potentials studied. These results point out the prevalence of the role of electron–hole pairs through surface plasmon activity to explain the obtained SERS spectra.

Intramolecular surfaces for vicinal proton–proton coupling constants 3JHH

Equations for the intramolecular surfaces of the 3JHH coupling constants in ethane, ethylene, and acetylene are formulated, and the corresponding coefficients are estimated from calculations at the DFT/B3LYP level. The chosen variables are changes in bond lengths, in the torsion angle φ between the coupled protons Ha and Hb, in bond angles, and in dihedral angles. The 3JHH surface of ethane is formulated as an extended Karplus equation with the coefficients of a truncated Fourier series on the torsion angle φ expanded as second-order Taylor series in the chosen variables taking into account the invariance of 3JHH under reflections and rotations of nuclear coordinates. Partial vibrational contributions from linear and square terms corresponding to changes in the geometry of the Ha − Ca − Cb − Hb fragment are important while those from cross terms are small with a few exceptions. The 3JHH surface of ethane is useful to predict contributions to 3JHH from changes in local geometry of derivatives but vibrational contributions are predicted less satisfactorily. The predicted values at the B3LYP/BS2 level of the 3JHH couplings (vibrational contributions at 300 K) from equilibrium geometries are 9.79 (−0.17) for acetylene, and 17.08 (1.93) and 10.73(0.93) for the trans and cis couplings of ethylene.

Exploring the interfacial neutral pH region of Pt(111) electrodes

The interfacial properties of Pt(111) single crystal electrodes have been investigated in the pH range 3 < pH < 5 in order to obtain information about the acidity of electrosorbed water. Proper experimental conditions are defined to avoid local pH changes while maintaining the absence of specifically adsorbed anions and preserving the cleanliness of the solution. For this purpose, buffer solutions resulting from mixtures of NaF and HClO4 are used. Total charge curves are obtained at different pHs from the integration of the voltammetric currents in combination with CO charge displacement experiments. Analysis of the composition of the interphase as a function of the pH provides information for the understanding of the notion of interfacial pH.

Electrochemical behaviour of activated carbons obtained via hydrothermal carbonization

Activated carbons were prepared by chemical activation of hydrochars, obtained by hydrothermal carbonisation (HTC) using low cost and abundant precursors such as rye straw and cellulose, with KOH. Hydrochars derived from rye straw were chemically activated using different KOH/precursor ratios, in order to assess the effect of this parameter on their electrochemical behaviour. In the case of cellulose, the influence of the hydrothermal carbonisation temperature was studied by fixing the activating agent/cellulose ratio. Furthermore, N-doped activated carbons were synthesised by KOH activation of hydrochars prepared by HTC from a mixture of glucose with melamine or glucosamine. In this way, N-doped activated carbons were prepared in order to evaluate the influence of nitrogen groups on their electrochemical behaviour in acidic medium. The results showed that parameters such as chemical activation or carbonisation temperature clearly affect the capacitance, since these parameters play a key role in the textural properties of activated carbons. Finally, symmetric capacitors based on activated carbon and N-doped activated carbon were tested at 1.3 V in a two-electrode cell configuration and the results revealed that N-groups improved the capacitance at high current density.

Grado en Geología de la Universidad de Alicante (2010-2014). Red de seguimiento

Con el comienzo del cuarto y último curso del grado en Geología en 2013-14, en la Facultad de Ciencias de la Universidad de Alicante se constituyó una red de seguimiento formada por todos los profesores coordinadores de semestre del citado grado. Esta red se enmarca en el programa de Redes de Investigación en Docencia Universitaria que la Universidad de Alicante ha implementado desde la implantación de los títulos de grado. El objetivo principal de esta red docente se ha centrado en realizar un seguimiento de la titulación en el marco de Sistema de Garantía Interno de Calidad (SGIC) y en desarrollar herramientas que favorezcan, tanto el buen funcionamiento del título, como la gestión interna del seguimiento del mismo. El método de trabajo se ha basado en reuniones en las que los miembros de la red han planteado y debatido los parámetros e indicadores de seguimiento de la red. Esta red ha trabajado conjuntamente con otras comisiones de la titulación como la Comisión del Grado en Geología (CGG), la Comisión de Trabajo de Fin de Grado en Geología (CTFGG) o la Comisión de Garantía de Calidad de la Facultad de Ciencias (CGCFC).

Molecularly imprinted silica films prepared by electroassisted deposition for the selective detection of dopamine

Dopamine (DA) can be detected by electrochemical oxidation in conventional electrodes. However, the presence of other oxidizable species (interferents) usually present in physiological fluids at high concentrations (like ascorbic acid) makes very difficult its electrochemical detection. In the present work, glassy carbon electrodes have been modified with molecularly imprinted silica (MIS) films prepared by electroassisted deposition of sol–gel precursors. The production of MIS films was performed by adding the template molecule (DA) to the precursor sol. The molecular impression of silica was assessed showing a high coherency allowing a filtering capacity in the molecular scale. The MIS-modified electrodes present a high selectivity for the detection of DA in neutral or acidic solutions. The MIS-modified electrodes allow the amperometric determination of dopamine in solutions containing ascorbic acid with molar ratios lower than 1:50,000.

Método POGIL para el Aprendizaje Cooperativo en Ciencias: Aplicación a la asignatura “Oceanografía Química”

Se muestra un método de aprendizaje cooperativo para una asignatura del Grado de Ciencias del Mar donde se aplica el método POGIL (Process-Oriented Guided Inquiry Learning). Los estudiantes aprenden los temas del curso siguiendo el ciclo del aprendizaje. En cada actividad se muestra un experimento o caso de estudio y se realizan preguntas para guiar a la comprensión del fenómeno observado. Tras la discusión y adquisición de los nuevos conceptos se formulan ejercicios para la aplicación de los mismos. Los grupos aprenden de forma autónoma pero el diseño de la actividad, menos libre que en métodos de aprendizaje similares (como el Aprendizaje Basado en Problemas) asegura la consecución de las competencias de conocimiento al final de la actividad. Se desarrollan además competencias genéricas: trabajo en equipo, comunicación efectiva y aprendizaje autónomo, entre otras. Se muestra un ejemplo de asignatura casi completamente desarrollada con este formato durante los 3 últimos cursos académicos. Se han realizado encuestas entre los alumnos con el fin de valorar el método educativo observándose que los alumnos se sienten más comprometidos con la asignatura y que tienen una mejor compresión de conceptos de química con este método que con clases tradicionales.

La elaboración del informe científico: los artículos científicos como referencia para la elaboración de informes de prácticas

El análisis, elaboración y presentación de resultados tanto experimentales como teóricos es una parte extremadamente importante en la investigación científica. Según nuestra experiencia docente, existe una notable carencia entre los estudiantes en su capacidad para la preparación de informes a partir de los trabajos experimentales realizados en el laboratorio. A veces esa carencia se agrava por no disponer de unos criterios claros de lo que debe aparecer en un informe científico. Por tanto, el trabajo de esta red será la búsqueda de metodologías para incentivar la obtención de competencias por parte del alumnado en lo que respecta a la preparación de informes de resultados de trabajos científicos, sean experimentales o de cálculo teórico. Se tomarán como guía los modelos universalmente utilizados en la bibliografía científica. De esta forma se logrará también familiarizar al alumnado en los cauces habituales de publicación de la investigación, usando ejemplos relacionados con el ámbito de la asignatura escogida (Cinética Química, 3er curso del Grado de Química).

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

The electro-oxidation of carbon materials enormously degrades their performance and limits their wider utilization in multiple electrochemical applications. In this work, the positive influence of phosphorus functionalities on the overall electrochemical stability of carbon materials has been demonstrated under different conditions. We show that the extent and selectivity of electroxidation in P-containing carbons are completely different to those observed in conventional carbons without P. The electro-oxidation of P-containing carbons involves the active participation of phosphorus surface groups, which are gradually transformed at high potentials from less-to more-oxidized species to slow down the introduction of oxygen groups on the carbon surface (oxidation) and the subsequent generation of (C*OOH)-like unstable promoters of electro-gasification. The highest-oxidized P groups (–C–O–P-like species) seem to distribute the gained oxygen to neighboring carbon sites, which finally suffer oxidation and/or gasification. So it is thought that P-groups could act as mediators of carbon oxidation although including various steps and intermediates compared to electroxidation in P-free materials.

Seguimiento del Grado en Geología (Facultad de Ciencias, Universidad de Alicante, curso 2015-16)

La Facultad de Ciencias de la Universidad de Alicante ha constituido una red de trabajo formada por los profesores coordinadores de semestre del Grado en Geología, así como por los coordinadores responsables de la titulación. Los objetivos de esta red son: Asegurar la ejecución efectiva de las enseñanzas conforme al contenido del plan de estudios del título verificado; detectar posibles deficiencias en su implementación, proponiendo recomendaciones y sugerencias de mejora; y evidenciar los progresos en el desarrollo del Sistema de Garantía Interno de Calidad (SGIC) tanto en lo relativo a la revisión de la aplicación del plan de estudios como a la propuesta de acciones para mejorar su diseño en la implantación. El método de trabajo se basa en reuniones en las que los miembros de la red plantearán y debatirán los parámetros e indicadores de seguimiento de la red. Cada coordinador llevará a cabo una investigación individualizada del semestre del que es responsable en coordinación con los miembros de su comisión. Asimismo, se participará en la elaboración de los informes de autoevaluación del título.

Evaluación continua a través del trabajo autónomo del estudiante

Durante el curso académico 2014-2015 se han introducido distintas mejoras en la metodología docente y en el sistema de evaluación de la asignatura Fundamentos Matemáticos de la Ingeniería II del primer curso del Grado en Ingeniería Civil de la Universidad de Alicante. Su objetivo es reducir el tiempo dedicado a la clase magistral en el desarrollo de la asignatura, en aras de fomentar la participación del alumnado. También se pretende conseguir un mayor aprovechamiento de las clases prácticas mediante la resolución autónoma de diversos ejercicios y problemas por parte de los alumnos, contando con la supervisión del profesorado. Este último aspecto es fundamental en las materias propias de las Matemáticas. En esta comunicación detallaremos las acciones específicas adoptadas con estos fines, tanto en la dinámica de las clases como en la forma de evaluación. Así mismo, se realizará un análisis cuantitativo y cualitativo de los resultados alcanzados y de las percepciones que profesores y alumnos tienen sobre los cambios introducidos.