Tailoring the Surface Chemistry of Activated Carbon Cloth by Electrochemical Methods

This paper presents a systematic study of the effect of the electrochemical treatment (galvanostatic electrolysis in a filter-press electrochemical cell) on the surface chemistry and porous texture of commercial activated carbon cloth. The same treatments have been conducted over a granular activated carbon in order to clarify the effect of morphology. The influence of different electrochemical variables, such as the electrode polarity (anodic or cathodic), the applied current (between 0.2 and 1.0 A) and the type of electrolyte (HNO3 and NaCl) have also been analyzed. The anodic treatment of both activated carbons causes an increase in the amount of surface oxygen groups, whereas the cathodic treatment does not produce any relevant modification of the surface chemistry. The HNO3 electrolyte produced a lower generation of oxygen groups than the NaCl one, but differences in the achieved distribution of surface groups can be benefitial to selectively tune the surface chemistry. The porous texture seems to be unaltered after the electro-oxidation treatment. The validity of this method to introduce surface oxygen groups with a pseudocapacitive behavior has been corroborated by cyclic voltammetry. As a conclusion, the electrochemical treatment can be easily implemented to selectively and quantitatively modify the surface chemistry of activated carbons with different shapes and morphologies.

Beyond the H2/CO2 upper bound: one-step crystallization and separation of nano-sized ZIF-11 by centrifugation and its application in mixed matrix membranes

The synthesis of nano-sized ZIF-11 with an average size of 36 ± 6 nm is reported. This material has been named nano-zeolitic imidazolate framework-11 (nZIF-11). It has the same chemical composition and thermal stability and analogous H2 and CO2 adsorption properties to the conventional microcrystalline ZIF-11 (i.e. 1.9 ± 0.9 μm). nZIF-11 has been obtained following the centrifugation route, typically used for solid separation, as a fast new technique (pioneering for MOFs) for obtaining nanomaterials where the temperature, time and rotation speed can easily be controlled. Compared to the traditional synthesis consisting of stirring + separation, the reaction time was lowered from several hours to a few minutes when using this centrifugation synthesis technique. Employing the same reaction time (2, 5 or 10 min), micro-sized ZIF-11 was obtained using the traditional synthesis while nano-scale ZIF-11 was achieved only by using centrifugation synthesis. The small particle size obtained for nZIF-11 allowed the use of the wet MOF sample as a colloidal suspension stable in chloroform. This helped to prepare mixed matrix membranes (MMMs) by direct addition of the membrane polymer (polyimide Matrimid®) to the colloidal suspension, avoiding particle agglomeration resulting from drying. The MMMs were tested for H2/CO2 separation, improving the pure polymer membrane performance, with permeation values of 95.9 Barrer of H2 and a H2/CO2 separation selectivity of 4.4 at 35 °C. When measured at 200 °C, these values increased to 535 Barrer and 9.1.

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.

Capillary microreactors based on hierarchical SiO2 monoliths incorporating noble metal nanoparticles for the Preferential Oxidation of CO

Novel hierarchical SiO2 monolithic microreactors loaded with either Pd or Pt nanoparticles have been prepared in fused silica capillaries and tested in the Preferential Oxidation of CO (PrOx) reaction. Pd and Pt nanoparticles were prepared by the reduction by solvent method and the support used was a mesoporous SiO2 monolith prepared by a well-established sol–gel methodology. Comparison of the activity with an equivalent powder catalyst indicated that the microreactors show an enhanced catalytic behavior (both in terms of CO conversion and selectivity) due to the superior mass and heat transfer processes that take place inside the microchannel. TOF values at low CO conversions have been found to be ∼2.5 times higher in the microreactors than in the powder catalyst and the residence time seems to have a noticeable influence over the selectivity of the catalysts designed for this reaction. The Pd and Pt flexible microreactors developed in this work have proven to be effective for the CO oxidation reaction both in the presence and absence of H2, standing out as a very interesting and suitable option for the development of CO purification systems of small dimensions for portable and on-board applications.

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.

Inmovilización de complejos organometálicos en soportes sólidos para aplicación en catálisis

La memoria de tesis titulada “Inmovilización de complejos organometálicos en soportes sólidos para aplicación en catálisis” presenta una serie de trabajos encaminados a la obtención de catalizadores híbridos, que sean estables, activos, selectivos y reutilizables en reacciones de hidrogenación e hidroformilación de olefinas. Para ello, se han estudiado diversos métodos para inmovilizar complejos metálicos en materiales carbonosos y sólidos inorgánicos: adsorción física, anclaje por formación de un enlace covalente e intercambio iónico. Estos catalizadores se han usado en las reacciones mencionadas, analizando sus propiedades catalíticas (actividad y selectividad), así como la robustez de los mismos y las posibilidades de reutilización.

Activated Carbon Fibre Monoliths for Hydrogen Storage

Porous adsorbents are currently investigated for hydrogen storage application. From a practical point of view, in addition to high porosity developments, high material densities are required, in order to confine as much material as possible in a tank device. In this study, we use different measured sample densities (tap, packing, compacted and monolith) for analyzing the hydrogen adsorption behavior of activated carbon fibres (ACFs) and activated carbon nanofibres (ACNFs) which were prepared by KOH and CO2 activations, respectively. Hydrogen adsorption isotherms are measured for all of the adsorbents at room temperature and under high pressures (up to 20 MPa). The obtained results confirm that (i) gravimetric H2 adsorption is directly related to the porosity of the adsorbent, (ii) volumetric H2 adsorption depends on the adsorbent porosity and importantly also on the material density, (iii) the density of the adsorbent can be improved by packing the original adsorbents under mechanical pressure or synthesizing monoliths from them, (iv) both ways (packing under pressure or preparing monoliths) considerably improve the storage capacity of the starting adsorbents, and (v) the preparation of monoliths, in addition to avoid engineering constrains of packing under mechanical pressure, has the advantage of providing high mechanical resistance and easy handling of the adsorbent.

Palladium and Bimetallic Palladium–Nickel Nanoparticles Supported on Multiwalled Carbon Nanotubes: Application to Carbon–Carbon Bond-Forming Reactions in Water

Palladium and bimetallic Pd–Ni nanoparticles (NPs) protected by polyvinylpyrrolidone were prepared by the reduction-by-solvent method and deposited on multiwalled carbon nanotubes (MWCNTs). The catalytic activity of these NPs to carbon–carbon bond-forming reactions was studied by using 0.1 mol % Pd loading, at 120 °C for 1 h and water as a solvent under ligand-free conditions. The Suzuki–Miyaura reaction took place quantitatively for the cross-coupling of 4-bromoanisole with phenylboronic acid, better than those obtained with potassium phenyltrifluoroborate, with Pd50Ni50/MWCNTs as a catalyst and K2CO3 as a base and TBAB as an additive, with good recyclability during 4 cycles with some Ni leaching. The Hiyama reaction of 4-iodoanisole with trimethoxyphenylsilane, under fluoride-free conditions using 50 % aqueous NaOH solution, was performed with Pd/MWCNTs as a catalyst in 83 % yield with low recyclability. For the Mizoroki-Heck reaction 4-iodoanisole and styrene gave the corresponding 4-methoxystilbene quantitatively with Pd50Ni50/MWCNTs using K2CO3 as a base and TBAB as an additive although the recycle failed. In the case of the Sonogashira-Hagihara reaction, Pd/MWCNTs had to be used as a catalyst and pyrrolidine as a base for the coupling of 4-iodoanisole with phenylacetylene under copper-free conditions. The corresponding 4-methoxytolane was quantitatively obtained allowing the recycling of the catalyst during 3 cycles.

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.

Diseño de Experimentación en Química Inorgánica sostenible

Se plantea al alumnado el análisis de la huella de carbono que tiene, en la actualidad, la asignatura práctica Experimentación en Química Inorgánica, con el objetivo de que busquen las posibilidades de sustitución y/o reducción de reactivos tóxicos y peligrosos en las prácticas de laboratorio que se imparten. Previamente, en base a dicho análisis, la red ha redactado las directrices que guiarán al alumno en sus búsquedas en bases de datos y su proposición de sustitución razonada de reactivos. Cada grupo de alumnos que trabaja en un proyecto particular de “Síntesis y caracterización de sustancias inorgánicas”, redacta un protocolo de actuación para eliminar/reducir el uso de reactivos peligrosos/contaminantes en su proyecto. Como colofón, se redacta un protocolo global para hacer más sostenible el proceso de enseñanza/aprendizaje de esta asignatura práctica. Además de trabajar el contenido específico de la asignatura, con esta metodología de aprendizaje, se pretende aumentar la capacidad del alumnado del Grado en Química para ser autónomo a la hora de proponer actuaciones fundamentadas que conduzcan a preservar el medio ambiente en su futuro ejercicio de la profesión de graduado en química.

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.

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.

Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

Switchable surfactant-assisted carbon nanotube coatings: innovation through pH shift

The inner surface of fused-silica capillaries has been coated with a dense/homogeneous coating of commercial multi-wall carbon nanotubes (MWCNTs) using a stable ink as deposit precursor. Solubilization of the MWCNTs was achieved in water/ethanol/dimethylformamide by the action of a surfactant, which can switch between a neutral or an ionic form depending on the pH of the medium, which thus becomes the driving force for the entire deposition process. Careful control of the experimental conditions has allowed us to selectively deposit CNTs on the inner surface of insulating silica capillaries by a simple, reproducible, and easily adaptable method.

Grado en Química: coordinación y seguimiento del curso 2014-15

En la red docente "Seguimiento del grado en Química", formada por los coordinadores de las comisiones de semestre de la Facultad de Ciencias y la coordinadora del grado en Química, se ha analizado la información extraída de las reuniones periódicas (al menos dos por semestre) de las ocho comisiones de semestre (correspondientes a los cuatro cursos del grado en Química). El objetivo es conseguir una coherencia tanto en la distribución de contenidos, como en las metodologías docentes y de evaluación de las materias que componen el plan de estudios del Grado en Química de la Universidad de Alicante. Los resultados de este trabajo están permitiendo identificar problemas y plantear propuestas de mejora en la organización docente de la titulación. El trabajo realizado por la red se está utilizando para elaborar el autoinforme para la reacreditación del grado en Química.