New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Using Surface Spectroscopy to Help Interpret STM Images of Chemisorbed Molecules: Application to the Study of the Hydrogenation of Ketones and a-Ketoesters on Pt

Depuis que la haute énantiopureté est nécessaire dans l’industrie pharmaceutique, les études visant à découvrir les mécanismes pour l’hydrogénation énantiosélective de cétones ou céto-esters sur les surfaces, et à rechercher de nouveaux et plus performants catalyseurs asymétriques, sont d’une grande importance. La microscopie à effet tunnel (STM), la spectroscopie infrarouge de réflexion-absorption, la spectroscopie de désorption à température programmée et la spectrométrie de photoélectrons induits par rayons X sont des méthodes performantes facilitant la compréhension des mécanismes de réaction. En plus de nous permettre de comprendre les mécanismes réactionnels, les études peuvent fournir des informations sur la dynamique des réactions en catalyse hétérogène ainsi que sur le développement de la théorie de la fonctionnelle de la densité (DFT) afin de calculer des interactions faibles dans les processus de surface. D’autres parts, les calculs DFT fournissent une aide essentielle à l’interprétation des données de STM et spectroscopie de surface. Dans cette thèse, certains cétones et céto-esters sur la surface de platine sont étudiées par les techniques sophistiquées mentionnées ci-dessus. Mes études démontrent que la combinaison de l’utilisation de la spectroscopie de routine, des nanotechnologies et de nombreux calculs élaborés, est une méthode efficace pour étudier les réactions à la surface car ces techniques explorent les différents aspects de la surface ainsi que s’entraident mutuellement lors de certaines interprétations.

SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

Comunicação entre médico dentista e técnico de prótese: uma perspectiva laboratorial

Dissertação para obtenção do grau de Mestre no Instituto Superior de Ciências da Saúde Egas Moniz

Mesoporous mixed Nb2O5-ZrO2 catalysts for dehydration of glucose into 5-hydroxymethylfurfural

Biomass is the world’s most important renewable carbon source, whose major component, carbohydrates, can be valorized by transformation into biofuels and high value-added chemicals. Among the latter, 5-hydroxymethylfurfural (HMF), obtained by C6 carbohydrates dehydration, is a versatile and key intermediate for the production of a large spectrum of biobased chemicals. Different catalytic systems have been evaluated for HMF production, mostly based on heterogeneous catalysis as alternative to the use of conventional mineral acids [1]. Moreover, niobium oxide has shown interesting properties as acid catalyst for dehydration of sugars [2-3]. On the other hand, the high surface area and large pore size of mesoporous solids make them suitable for many catalytic processes. In the present work, the dehydration of glucose to HMF has been evaluated by using different mesoporous mixed Nb2O5-ZrO2 in a biphasic water–Methyl Isobutyl Ketone (MIBK) solvent system to avoid the HMF degradation. Different experimental parameters, such as reaction temperature and time, as well as the addition of CaCl2 have been studied in order to maximize the HMF yield.N2 adsorption-desorption isotherms have corroborated the mesostructured character of catalysts, being all isotherms of Type IV according to the IUPAC classification. BET surface area decreases for catalysts with higher Zr content (Table 1). Likewise, pore volume and average pore diameter values diminish after Zr incorporation. Concerning the acid properties, a clear correlation between Nb and acidity can be observed, in such a way that total acidity, as deduced from NH3-TPD, decreases when the Zr content rises, and consequently the amount of Nb is reduced.These mesoporous Nb-Zr catalysts have been tested in the dehydration of glucose to HMF at 175 ºC under batch operation in aqueous solution, using MIBK as co-solvent. It can be observed that both glucose conversion and HMF yield increase with the Nb content, being maximum (90% and 36%, respectively) after 90 minutes for Nb2O5. This trend changes when CaCl2 is added to the reaction medium, improving the catalytic performance of mixed oxides and ZrO2, but Nb2O5 maintains similar results than without salt addition. This could be justified by the interaction between CaCl2 and Lewis acid sites, since zirconium oxide possesses a higher amount of this acid sites type.

De la formación permanente del profesorado a la formación dialógica de la comunidad: análisis de una tertulia pedagógica comunitaria

Esta tesis presenta una investigación de carácter teórico y empírico sobre una modalidad de formación continua denominada Tertulia Pedagógica Dialógica (TPD). En ella se incorporan distintos agentes educativos para leer y debatir, a través de un diálogo igualitario, sobre textos que muestran cuáles son aquellas actuaciones educativas que logran éxito escolar para todo el alumnado, mejoran la convivencia y están contribuyendo a la superación de la desigualdad educativa y social (actuaciones educativas de éxito –AEE-). Entraría dentro de lo que algunos autores y autoras denominan una formación basada en evidencias (R. Flecha, Racionero, Tintoré, & Arbós, 2014; Wineburg, 2006). Junto a ellas, se estudian las teorías que las sustentan y que son la clave de su eficacia; teorías desarrolladas por los más reconocidos autores y autoras en múltiples campos como la educación, la psicología, la sociología o la política (Freire, Bruner, Habermas, Chomsky, Vygotski, Mead…). Este conocimiento científico e interdisciplinar garantiza un riguroso soporte teórico que, no solo tiene en cuenta la eficacia de las actuaciones, sino también, un profundo compromiso ético por la mejora educativa y social de los colectivos más vulnerables. El objetivo principal de esta investigación es identificar las características y comprobar las aportaciones que las Tertulias Pedagógicas Dialógicas pueden tener en el contexto de una formación comunitaria, las interacciones que se generan entre las y los distintos agentes participantes y si contribuyen al desarrollo de actuaciones conjuntas encaminadas a la mejora educativa (AEE). Por tanto, el enfoque de esta tesis pretende responder a una importante demanda que se hace en la actualidad a las ciencias sociales: ir más allá de la mera descripción y el diagnóstico de las situaciones y aportar soluciones a los principales retos sociales. En nuestro caso, tratamos de identificar aquellas barreras que encuentran los distintos agentes sociales en sus procesos de formación y relación así como los elementos transformadores que aporta esta formación para posibilitar que se establezcan relaciones de colaboración, que reviertan en la mejora educativa...

Análisis de los posibles efectos del TLC con Estados Unidos en el subsector del maíz

En el marco del desarrollo del sector primario en Colombia, se observa la existencia de una serie de situaciones o factores adversos que le impiden alcanzar su productividad y competitividad, entre los cuales destacan los altos costos de la materia prima e insumos utilizados en los procesos productivos de siembra y cosecha, la inexistencia de políticas públicas que garanticen un verdadero apoyo al campesinado colombiano, como los subsidios y/o estrategias de protección a la producción nacional, estas últimas, como barrera a la entrada en grandes volúmenes de productos importados, resultantes de los acuerdos internacionales donde se les da mayor participación a los productos importados, como ha sido en los últimos años, los provenientes de Canadá y Estados Unidos, este último, con la firma del TLC. Lo anterior ha coadyuvando a una reducción en las áreas de cultivo, así como en el rendimiento por hectáreas; como es el caso de la agrocadena de cereales, entre los que destaca el maíz amarillo, el cual ha experimentado un alto incremento en su volumen de importación, resultado de los excedentes exportables dados en la producción agrícola norteamericana, siendo los subsidios que a través de la ley Farm Bill, el gobierno norteamericano le otorga a los productores agropecuarios, un incentivo importante para tal fin. Con base en esto, los precios internacionales de comercialización del maíz amarillo han presentado una tendencia de decrecimiento, imposibilitando a los productores colombianos afrontar esta situación. Por medio de esta investigación se busca evaluar y esclarecer los posibles efectos del TLC de Colombia con Estados Unidos sobre los productores de maíz, y así mismo porporcionar alternativas de solución tanto para los campesinos como para el gobierno, identificando las principales variables que afectan la producción del cereal

Estudio del tratado de libre comercio Colombia – Estados Unidos: Iowa, Kansas, Kentucky, Luisiana y Maine

Con el proceso de globalización que se evidencia actualmente, el comercio entre países ha sido uno de los factores más relevantes a través del tiempo y Colombia no ha sido excluyente a esta situación. Es por la importancia del asunto, que la Escuela de Administración dentro de sus múltiples proyectos de investigación busca la identificación de oportunidades para PYMES colombianas en mercados extranjeros, específicamente en Estados Unidos, asumiendo los retos que trae consigo un Tratado de Libre Comercio, las implicaciones en cuanto a los procesos de intercambio (importaciones y exportaciones) en sus diversos ámbitos y el impacto que genera dicho proceso en la balanza comercial colombiana. Debido a esto, se ha propuesto el desarrollo de un trabajo de grado que analice el Tratado de Libre Comercio (TLC) entre Colombia y Estados Unidos, enfocándose en los perfiles de cada mercado y las necesidades de los mismos, con el fin de identificar oportunidades generadas desde su puesta en marcha. En busca de un análisis detallado, el trabajo en mención hace énfasis en cinco estados de Estados Unidos (Iowa, Kansas, Kentucky, Luisiana y Maine) y los 32 departamentos de Colombia. Con el objetivo de realizar un análisis más efectivo se tomaron en cuenta las características de cada mercado y su relación comercial. A partir del previo proceso de investigación, se pretende identificar y definir oportunidades comerciales que evidencian una evolución comercial (mayor número de importaciones y exportaciones). Dichas oportunidades identificadas son el resultado de un análisis cualitativo tras desarrollar matrices de los principales diez productos más demandados por los Estados mencionados y los principales productos ofertados por los departamentos colombianos. Gracias a lo que enmarca un TLC dentro de un proceso de negociación, se proyecta identificar según las necesidades de las partes, es decir, oferta y demanda de bienes y/o 9 servicios, cada una de las oportunidades claves para los comerciantes nacionales que se involucran dentro del acuerdo aprobado.