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Diesel #2 is used to heat nearly 400,000 dwellings in Virginia. Home heating oil released from leaking underground tanks located adjacent to homes and residing in unsaturated soil adjacent to houses poses a potentially serious health risk. Specifically, the migration of hazardous vapors into buildings, known as vapor intrusion, can negatively impact indoor air quality in homes and public buildings (USEPA 2015). In this look-back study, we assessed the potential for petroleum vapor intrusion by sampling soil vapor at 25 previously remediated spill sites. Residual contaminants, in particular total petroleum hydrocarbons (TPH) and naphthalene, were detected in approximately 1/3 of the samples. Concentration levels were correlated to site variables (building type, remediation time, physiographic region) including previous abatement measures. Spill category as assigned by the remediation contractor was investigated in conjunction with these three site variables. Remediation time was the most promising predictive site variable, with visible trends downward in DEQ Category 2 sites with increased remediation time. Higher contaminant concentrations were found near basement-style dwellings, which we hypothesize is due to the wall of the basement blocking horizontal migration of contaminants and the flow of oxygen to the release source zone. We found that many sites exceeded the sub-slab risk target threshold in naphthalene concentration, which has negative implications on previous abatement strategy efficacy. / Master of Science

L’évaluation de l’exposition aux composés organiques volatils (COV) recourt couramment à l’analyse des métabolites urinaires en assumant qu’aucune interaction ne survient entre les composés. Or, des études antérieures ont démontré qu’une inhibition de type compétitive survient entre le toluène (TOL), l’éthylbenzène (EBZ) et le m-xylène (XYL). Le chloroforme, qui est également un solvant métabolisé par le CYP2E1, se retrouve souvent en présence des autres COV dans les échantillons de biosurveillance. La présente étude visait donc à évaluer si le chloroforme (CHL) peut lui aussi interagir avec ces COV et évaluer ces interactions au niveau de l’excrétion des biomarqueurs urinaires associés, soit l’o-crésol, l’acide mandélique et l’acide m-méthylhippurique pour TOL, EBZ et XYL respectivement. Afin d’obtenir des données humaines, cinq volontaires ont été exposés par inhalation à différentes combinaisons de COV (seuls et mélanges binaires ou quaternaires) où la concentration de chacun des composés était égale à 1/4 ou 1/8 de la valeur limite d’exposition (VLE) pour une durée de 6h. Des échantillons d’air exhalé, de sang et d’urine ont été récoltés. Ces données ont ensuite été comparées aux modèles pharmacocinétiques à base physiologique (PCBP) existants afin de les ajuster pour l’excrétion urinaire. Certaines différences ont été observées entre les expositions aux solvants seuls et les coexpositions, mais celles-ci semblent majoritairement attribuables aux remplacements de participants à travers les différentes expositions. Les valeurs de Vmax pour EBZ et CHL ont été optimisées afin de mieux prédire les niveaux sanguins de ces COV. À l’exception du modèle pour EBZ, tous les paramètres pour l’excrétion urinaire ont été obtenus à partir de la littérature. Les modèles adaptés dans cette étude ont permis de simuler adéquatement les données expérimentales. / Evaluation of volatile organic compounds (VOC) exposure commonly resorts to urinary metabolite analyses, assuming that no interaction occur between coexposed chemicals. However, previous studies have reported competitive inhibition between toluene (TOL), ethylbenzene (EBZ) and m-xylene (XYL). Chloroform, which is also metabolized by CYP2E1, is also often found in human biomonitoring samples along with the mentioned VOCs. The goal of the present study was to evaluate if chloroform (CHL) can interact with previous VOC and to evaluate those interactions at the urinary biomarker excretion level for corresponding metabolites, namely o-cresol, mandelic acid and m-methylhippuric acid for TOL, EBZ and XYL respectively. To obtain human data, five male volunteers were exposed by inhalation to different VOC combinations (single and binary or quaternary mixtures) where concentration of each chemical was equal to 1/4 or 1/8 of the threshold limit value (TLV) for 6h. Exhaled air blood and urine samples were collected. These data were then compared with existing physiologically based pharmacokinetic (PBPK) model predictions for adjustment for urinary excretion. Some differences were observed between single and mixed exposures but they may be mainly related to volunteer replacements throughout experiments. Vmax values for EBZ and CHL were optimized to better fit blood data. Except for EBZ model, all urinary excretion parameters were taken from the literature. Models adapted in the present study adequately simulated experimental data.

Afin de répondre aux demandes des industriels de nouveaux matériaux poreux sont testés pour de nouvelles applications ou pour améliorer les procédés existants. Les adsorbants de types Metal Organic Frameworks(MOFs) ont des structures construites à partir d'unités inorganiques reliées entre elles par des ligands organiques. La possibilité de varier ces deux entités, offre une grande diversité de structures avec des cavités de tailles contrôlées. L'objectif de cette thèse a été d'évaluer les performances des MOFs pour l'adsorption de composés organiques et de comprendre les mécanismes d'adsorption. Les deux problématiques sélectionnées sont d'intérêt pour l'industrie pétrochimique. La séparation du para-xylène des autres isomères du xylène et de l'éthylbenzene, permets de répondre à la demande de matière première pour la synthèse du polytéréphtalate d'éthylène. L'adsorption des composés azotés et soufrés (teneur fixée par des législations), permets la purification de carburants. Notre étude thermodynamique est basée sur la réalisation d'isothermes d'adsorption et la détermination d'enthalpies d'adsorption par microcalorimétrie en phase liquide. L'adsorption des vapeurs des xylènes purs a été étudiée pour comprendre l'effet du solvant. Une grande variété de comportement a été observée selon les structures des MOFs. Nous avons par exemple mis en évidence l'effet de l'empilement moléculaire des isomères du xylène sur la sélectivité des MOFs. Nous avons démontré que la flexibilité des MOFs intervient sur les interactions au cours de l'adsorption des xylènes. Nous avons mis en évidence une sélectivité des MOFs possédant un centre métallique insaturé en faveur des composés azotés / In order to meet the industrials requirements, new porous materials are tested for new applications or to improve existing processes. The Metal Organic Frameworks (MOFs) are hybrids crystalline compounds made up of clusters (or chains) of metal ions coordinated by organic linkers to form three dimensional structures. The ability to vary these two entities offers to MOFs a wide variety of organized structure with pore sizes controlled. The aim of this thesis was to evaluate the MOF performances for the adsorption of organic compounds and also understand the related adsorption mechanism. The two selected issues are of interest for the petrochemical industry. The para-xylène separation from the other xylene isomers (ortho, meta) and ethylbenzene, allows to meet the demand for raw materials in the polyethylene terephthalate (PET) synthesis. The nitrogen and sulphur compounds adsorption allows the purification of fuels (sulphur content set by legislation). We present a thermodynamic study of adsorption from solution based on the determination of adsorption isotherms by depletion method and adsorption enthalpies by microcalorimetry. The pure xylenes vapour adsorption was also studied to understand the solvent effect. A wide variety of behaviour has been observed depending on MOF structures. For example we demonstrated the effect of xylene isomers molecular packing on MOF selectivity. Furthermore we have shown that the MOF structure flexibility influence the interactions involved during xylene isomers adsorption. We also demonstrated that MOF with unsaturated metallic centres present selectivity for nitrogen compounds (Lewis acid/base).

Made available in DSpace on 2014-07-29T15:12:50Z (GMT). No. of bitstreams: 1 carlos rangel.pdf: 2728067 bytes, checksum: fb16fe4d020ade6680388acadc30184b (MD5) Previous issue date: 2010-02-09 / In this work were synthesized catalysts supported on activated carbons, which were obtained by carbonization of a polymer matrix. The precursor of activated carbon was the sulfonated styrene-divinylbenzene copolymer, which was synthesized by suspension polymerization in the presence of inert diluents to produce a macroporous network structure. The chemical modification was performed by sulfonation with concentrated sulfuric acid in the presence of dichloroethane. The supported catalysts were obtained by two routes. In the first one oxides were co-precipitated on the modified copolymer, and then the polymer was subjected to heat treatment and carbonization followed by activation. In the second route, the copolymer was first carbonized and subjected to activation, and then oxides were produced by co-precipitation of metalic ions. In both cases the coprecipitation involved two steps: incorporation of iron and cobalt ions through an ion exchange process and then coprecipitation in alkaline and oxidizer medium. The heat treatment consists of a heating step at 250 ° C in air atmosphere, carbonization at 900 ° C under nitrogen atmosphere and activation at 900 º C with a flow of nitrogen saturated with water vapor. The influence of the percentage of cobalt relative to iron in the material properties as well as catalytic activity in the reaction of dehydrogenation of ethylbenzene was investigated. The materials were characterized by their magnetism, infrared spectroscopy, X-ray diffraction, chemical analysis, Mossbauer spectroscopy, optical microscopy, measurements of porosity by nitrogen adsorption and catalytic activity in the reaction of catalytic dehydrogenation of ethylbenzene with water vapor. It was observed that the materials prepared by the two different routes have properties quite different as the amount of metal incorporated, the formation of oxides and textural properties. It was observed that the thermal treatments influence dramatically in the oxidation state of iron due to various reactions of oxidation and reduction occurring during the stages of synthesis and catalytic evaluation. The catalysts obtained by the two routes had better textural properties than the commercial catalyst. All supported catalysts obtained were active in the reaction of dehydrogenation of ethylbenzene. Even the support of activated carbon oxidized with nitric acid showed catalytic activity. Among the catalysts synthesized, those obtained by the second route had the best conjugated results of conversion and selectivity for the reaction, especially those synthesized with oxidized activated carbon. These catalysts are the most promising due their textural properties and surface functional groups of activated carbon. / Neste trabalho foram sintetizados catalisadores suportados em carvões ativados, que foram obtidos por meio da carbonização de uma matriz polimérica. O precursor do carvão ativado foi o copolímero de estireno e divinilbenzeno sulfonado, que foi sintetizado por meio de polimerização em suspensão, na presença de diluentes inertes para a produção de uma estrutura macroporosa e reticulada. A modificação química por sulfonação foi realizada com ácido sulfúrico concentrado na presença de dicloroetano. Os catalisadores suportados foram obtidos por duas rotas. Na primeira delas os óxidos foram coprecipitados sobre o copolímero modificado, e em seguida o polímero foi submetido a tratamentos térmicos e carbonização, e posterior ativação. Na segunda rota, o copolímero foi primeiramente carbonizado e submetido a ativação, e em seguida os óxidos foram produzidos pela coprecipitação de íons metálicos. Em ambos os casos a coprecipitação envolveu duas etapas: incorporação dos íons ferro e cobalto por meio do processo de troca iônica e em seguida coprecipitação em meio alcalino oxidante. O tratamento térmico consiste em uma etapa de aquecimento a 250 ºC em atmosfera de ar, a carbonização a 900 ºC em atmosfera de nitrogênio e a ativação a 900 ºC com um fluxo de nitrogênio saturado com vapor de água. Investigou-se durante a preparação dos catalisadores a influência do percentual de cobalto em relação ao ferro nas propriedades do material, e consequentemente em sua atividade catalítica na reação de desidrogenação do etilbenzeno. Os materiais foram caracterizados por seu magnetismo, espectroscopia de infravermelho, difração de raios X, análise química, espectroscopia de Mössbauer, microscopia ótica, medidas de porosidade por adsorção física de nitrogênio e atividade catalítica na reação de desidrogenação catalítica do etilbenzeno com vapor de água. Observou-se que os materiais preparados pelas duas rotas distintas apresentaram propriedades bastante diferentes quanto a quantidade de metal incorporado/coprecipitado, a formação dos óxidos e as propriedades texturais. Evidenciou-se ainda que os tratamentos térmicos influenciam drasticamente nos óxidos formados devido a várias reações de oxidação e redução que ocorrem durante as etapas de síntese e mesmo na avaliação catalítica. Os catalisadores obtidos pelas duas rotas apresentaram propriedades texturais superiores as do catalisador comercial. Todos os catalisadores suportados obtidos foram ativos na reação de desidrogenação do etilbenzeno. Até mesmo o suporte de carvão ativado oxidado com ácido nítrico apresentou atividade catalítica. Dentre os catalisadores sintetizados, os obtidos pela segunda rota apresentaram os melhores resultados conjuntos de conversão e seletividade para a reação, principalmente os sintetizados com carvão ativado oxidado. Esses catalisadores são os mais promissores devido as propriedades texturais e aos grupos funcionais superficiais do carvão ativado.

Risk Analysis of Construction Chemicals Storge Diplom Thesis, Institute of Metrollogy and Quality Assurance Testing, Brno University of Technology, Faculty of Mechanical Engineering This diploma thesis focuses on risk assessment and possible assessment measure necessary when the amount of storage load containing Ethylbenzen increases by 300 percent.

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from both anthropogenic and biogenic emission sources in the urban surface layer. We describe a new relaxed eddy accumulation system combined with a dual-channel gas chromatography - flame ionization detection used for volatile organic compound (VOC) flux measurements in the urban area, focusing on the results of selected anthropogenic VOCs, including benzene, toluene, ethylbenzene and xylenes (BTEX), and biogenic VOCs including isoprene and its oxidation products, methacrolein (MACR) and methyl vinyl ketone (MVK). We present diurnal variations of concentrations and fluxes of BTEX, and isoprene and its oxidation products during summer time (May 22 - July 22, 2008) and winter time (January 1 - February 28). The measured BTEX values exhibited diurnal cycles with a morning peak during weekdays related to rush-hour traffic and additional workday daytime flux maxima for toluene and xylenes in summer time. However, in winter time there was no additional workday daytime peaks due mainly to the different flux footprints between the two seasons. A comparison with different EPA National Emission Inventories (NEI) with our summer time flux data suggests potential underestimates in the NEI by a factor of 3 to 5. The mixing ratios and fluxes of isoprene, MACR and MVK were measured during the same time period in summer 2008. The presented results show that the isoprene was affected by both tail-pipe emission sources during the morning rush hours and biogenic emission sources in daytime. The observed daytime mixing ratios of isoprene were much lower than over forested areas, caused by a comparatively low density of isoprene emitters in the tower's footprint area. The average daytime isoprene flux agreed well with emission rates predicted by a temperature and light only emission model (Guenther et al., 1993). Our investigation of isoprene's oxidation products MACR and MVK showed that both anthropogenic and biogenic emission sources exist for MACR, while MVK was strongly dominated by a biogenic source, likely the isoprene oxidation between the emission and sampling points.

Student Number: 9503012G Master of Science. School of Geography, Archaeology and Environmental Studies / A brown haze which builds-up over Cape Town under calm and cold weather conditions causes public concern. The brown haze is thought to be due to the gaseous and particulate emissions from the city, industries, traffic and townships in the Cape Town region. Volatile organic carbon (VOCs) compounds are an important component of the haze layer particularly because of their reactivity. VOCs play an important role in the carbon budget and radiation balance, regional oxidant balance, and in the distribution of ozone and other reactive gases, both at the regional and global scale. In this study the variation in ambient VOC concentrations during brown and non-brown haze days over Cape Town during July and August 2003 were characterised. Ambient air samples were collected in evacuated stainless steel canistes from the South African Weather Service (SAWS) research aircraft (Aerocommander, ZS-JRB) and later analysed by gas chromotography equipped with a flame ionisation detector (GC-FID). Benzene, toluene, ethylbenzene and xylene (BTEX) were the specific VOCs targeted for this study. Comparable meteorology data was also collected to determine the effects of wind field and atmospheric stability on BTEX concentrations.

En av de vanligaste föroreningarna i mark och grundvatten är aromatiska kolvä- ten såsom bensen, toluen, etylbensen och xylener. Dessa härstammar från ex. ben- sin och har läckt ut till omgivande miljö från drivmedelsanläggningar. I stället för schaktning och bortforsling av de förorenade jordmassorna som mest förekom- mande ex situ-saneringsmetod behövs mer forskning kring in situ-saneringsmetoder där föroreningen alltså kan angripas på plats. I denna rapport undersöks förhöjd biologisk nedbrytning genom att redogöra för de önskvärda (bio)kemiska reak- tionerna i marken, de parametrar som styr den biologiska nedbrytningen samt huruvida dessa parametrars inverkan har kunnat påvisas i tre stycken fallstu- dier där in situ-sanering utförts vid drivmedelsanläggningar. Studien kommer fram till ett antal primära (ursprungliga) variabler såsom föroreningen i fråga, jordtätheten och klimatet, samt ett antal sekundära (förändringsbara) variabler såsom oxidationsmedlet, mikroorganismerna, näringsämnena och markvattnet. Dessa presenterades sedan i en schematisk skiss som visar hur de växelverkar med parametrarna för optimal biologisk nedbrytning, vilka visade sig ha vissa optimala värden. Dessa konstaterades vara föroreningshalten (<5-10 viktprocent torr jord), pH-värdet (6-9), temperaturen (20-35◦C), vattenmättnaden (40-80%), syrehalten (> 2 500 viktprocent kolväten), C:N:P-kvoten (100:10:1) samt koncent- rationen mikroorganismer (> 103 CFU/ml). När de olika parametrarnas inverkan  i fallstudierna undersöktes kunde slutsatsen dras att det skulle behövas ytterliga- re data och mätningar vid varje sanering för att kunna garantera att parametrarna varit inom sina respektive optimala värden. / One of the many goals for a sustainable living and a healthy environment is the reduction of toxic substances in soil and groundwater. Within this ambit, one of the most common pollutants is aromatic hydrocarbons such as benzene, tolue- ne, ethylbenzene and xylenes (BTEX) which are spread from e.g. filling stations for fuel as they are constituents of petrol. These are volatile and can constitute a risk for humans and the environment as they percolate through the soil and groundwater resources as well as can exfiltrate from the ground to surrounding buildings and pollute the indoor air. Once these pollutants are present in the soil, the site needs to be remediated, something which is mainly done ex situ by exca- vating the polluted masses to be sent to a treatment facility. An alternative to this is in situ remediation where the pollution can be treated without being excavated and thus having a smaller impact on the environment.  In this report, one of these techniques called enhanced biodegradation was studied, which implies the application of oxidisers to faciliate microbial activities. It investigated (1) how this remediation technique works and what (bio)chemical reactions are desired in the soil; (2) what are the principal parameters that enable this remediation process and how do they interact with the surrounding factors, and (3) whether the impact of these parameters can be estimated in three case studies where this technique has been used. The three case studies were filling stations located in Sweden, having similar pollutants and geology, and two diffe- rent oxidisers had been used.  The study resulted in the identification of a number of primary (initial) varia- bles such as the pollutant characteristics, the soil density and the climate; as well as a number of secodnary (modifiable) variables such as the oxidiser, microorga- nisms, nutrients and soil moisture. These were then presented in a scheme which shows how their interactions with the parameters for optimal biodegradation. Each parameter was found to have a certain optimum such as the concentration of hydrocarbons (<5-10 mass percent of the dry soil) , pH value (6-9), tempe- rature (20-35◦C), soil water saturation (40-80%), oxygen concentration (> 2,500 mass percent of the hydrocarbons), C:N:P ratio (100:10:1) as well as concentration of microorganisms (> 103 CFU/ml). A negative correlation could be identified between the soil density and the oxygen concentration in the soil, as well as a po- sitive correlation between the soil water saturation in the and the soil moisture, alternatively additional water via irrigation. The impact of each parameter in the case studies of in situ remediation was assessed and the it could be concluded that they would need additional data and measurements for most parameters in order to guarantee that they are within the respective optima.

[ES] Toda esta disertación ha utilizado la química computacional como herramienta fundamental para el análisis científico. Por ello, en el Capítulo 2 se explican los modelos y métodos teóricos sobre este tema. La primera parte del capítulo se centra en los fundamentos de la química cuántica y, en concreto, se explica con detalle la Teoría del Funcional de la Densidad la cual constituye la base de los métodos computacionales aplicados. En esta sección, las nociones básicas del método Hartree-Fock sirven de prólogo a la DFT. El Capítulo 3 presenta los primeros resultados de este trabajo correspondientes a la reacción de metanol a olefinas catalizada por diferentes zeolitas con cavidades de poro pequeño. Esta reacción es un proceso industrial relevante que produce olefinas de cadena corta como eteno (C2=), propeno (C3=) y buteno (C4=) a escala industrial a partir de la biomasa. El sistema catalítico comprende tanto la estructura inorgánica de la zeolita que contiene los sitios ácidos Brønsted como las especies orgánicas confinadas, que forman la "hydrocarbon pool" y producen olefinas ligeras mediante pasos sucesivos de metilación y craqueo. Hemos centrado nuestros esfuerzos en comprender la naturaleza de la "hydrocarbon pool", una molécula de benceno polimetilada, y sus mecanismos de reacción para poder discernir entre ellos e identificar los catalizadores adecuados para mejorar la producción de propeno o eteno en función de la topología de cada cavidad zeolitica. Hemos podido identificar el grado de metilación de la "hydrocarbon pool" como el factor clave para potenciar el mecanismo de la ruta "paring", donde el propeno es el producto mayoritario, o el mecanismo de la ruta "side-chain", siendo el eteno el producto predominante. Este hallazgo nos permite establecer una relación entre la estabilización de los dos intermedios clave y la selectividad experimental observada con un alto grado de correlación. En el Capitulo 4 presentamos una nueva herramienta para el estudio de reacciones competitivas catalizadas por zeolitas. Utilizando un cribado computacional rápido con "force fields" para los intermedios clave de la reacción y un detallado estudio mecanístico usando la teoría del funcional de la densidad somos capaces de reconocer y cuantificar sutiles diferencias en la estabilización de intermedios y estados de transición dentro de huecos microporosos similares, aproximándonos así al nivel de reconocimiento molecular de las enzimas. Con estas herramientas somos capaces de seleccionar como catalizador una zeolita que obstaculice el mecanismo "alkyl-transfer" reduciendo la producción de eteno no deseado y potenciando al mismo tiempo el mecanismo "diaryl-mediated pathway". También somos capaces de obstaculizar la desproporción de dietilbenceno, una ruta no deseada del mecanismo "diaryl-mediated pathway" que conduce a la producción de trietilbenceno, mientras que se favorece la transalquilación de dietilbenceno aumentando el rendimiento obtenido de etilbenceno. en la primera sección del Capítulo 5, estudiamos la afinidad energética de cationes alquilamonio comercialmente disponibles con ligeras diferencias en sus grupos alquilo, TEA, MTEA y DMDEA, para la síntesis de CHA y sus efectos sobre la calidad del material obtenido. Evaluamos las energías de interacción entre la zeolita y el catión de diferentes combinaciones de agentes directores y cationes Na+ con métodos DFT periódicos pudiendo distinguir pequeños efectos de estabilización causados por ligeras diferencias estructurales entre moléculas que repercuten en la estructura final sintetizada. Durante la segunda sección del Capítulo 5, identificamos las características estructurales de diferentes agentes directores de estructura para la síntesis de AEI que mejoran las probabilidades de dispersión del Al en posiciones tetraédricas distintas de T1 obteniendo un catalizador AEI diferente de los sintetizados clásicamente. / [CA] Tota aquesta dissertació utilitza la química computacional com eina fonamental per a l'anàlisi científica. Per això, en el Capítol 2 s'expliquen els models i mètodes teòrics sobre aquest tema. La primera part del capítol es centra en els fonaments de la química quàntica i, en concret, s'explica amb detall la Teoria del Funcional de la Densitat la qual constitueix la base dels mètodes computacionals aplicats. En aquesta secció, les nocions bàsiques del mètode Hartree-Fock serveixen de pròleg a la DFT. El Capítol 3 presenta els primers resultats d'aquest treball corresponents a la reacció de metanol a olefines catalitzada per diferents zeolites amb cavitats de porus petit. Aquesta reacció és un procés industrial rellevant que produeix olefines de cadena curta com etè (C2=), propè (C3=) i butè (C4=) a escala industrial a partir de la biomassa. El sistema catalític comprèn tant l'estructura inorgànica de la zeolita que conté els llocs àcids Brønsted com les espècies orgàniques confinades, que formen la "hydrocarbon pool" i produeixen olefines lleugeres mitjançant passos successius de metilació i craqueig. Hem centrat els nostres esforços en comprendre la naturalesa de la "hydrocarbon pool", una molècula de benzè polimetilada, i els seus mecanismes de reacció per a poder discernir entre ells i identificar els catalitzadors adequats per millorar la producció de propè o etè en funció de la topologia de cada cavitat zeolitica. Hem pogut identificar el grau de metilació de la "hydrocarbon pool" com el factor clau per a potenciar el mecanisme de la ruta "paring", on el propè és el producte majoritari, o el mecanisme de la ruta "side-chain", sent l'etè el producte predominant. Al Capítol 4 presentem una nova eina per a l'estudi de reaccions competitives catalitzades per zeolites. Utilitzant un cribratge computacional ràpid amb "force fields" per als intermedis clau de la reacció i un detallat estudi mecanístic amb la teoria del funcional de la densitat som capaços de reconèixer i quantificar subtils diferències en l'estabilització d'intermedis i estats de transició dins de buits microporosos similars, aproximant-nos així al nivell de reconeixement molecular dels enzims. en la primera secció del Capítol 5, estudiem l'afinitat energètica de cations alquilamoni comercialment disponibles amb lleugeres diferències als seus grups alquil, TEA, MTEA i DMDEA, per a la síntesi de CHA i els seus efectes sobre la qualitat del material obtingut. Avaluem les energies d'interacció entre la zeolita i el catió entre diferents combinacions d'agents directors i cations Na+ amb mètodes DFT periòdics podent distingir petits efectes d'estabilització causats per lleugeres diferències estructurals entre molècules que repercuteixen en l'estructura final sintetitzada. Durant la segona secció del Capítol 5, identifiquem les característiques estructurals de diferents agents directors d'estructura per a la síntesi d'AEI que milloren les probabilitats de propagació de l'Al a través de posicions tetrahedriques diferents de T1 obtenint un catalitzador AEI diferent dels sintetitzats clàssicament. / [EN] Computational chemistry has been used as the fundamental tool during the whole work. Therefore, the theoretical models and methods on this subject are explained in Chapter 2. The first part sketches the fundamentals of quantum chemistry and specifically explains the Density Functional Theory that constitutes the basis of the computational methods applied. In this section, basic notions of the Hartree-Fock method serve as prologue for DFT after which more practical aspects are elucidated. Chapter 3 presents the first results of this work corresponding to the methanol to olefins reaction catalysed by different small-pore cage-like zeolites. This reaction is a relevant process that produces short chain olefins such as ethene, propene and butene at industrial scale from biomass. The catalytic system comprises both the zeolite inorganic framework containing the Brønsted acid sites and the confined organic species, that form the hydrocarbon pool and produce light olefins by successive methylation and cracking steps. Our efforts are focused on understanding the nature of the hydrocarbon pool, a polymethylated benzene molecule, and its reaction mechanisms in order to be able to discern between them and identify the proper catalysts to enhance propene or ethene production based on each zeolite cavity topology. We have been able to identify the hydrocarbon pool methylation degree as the key factor to enhance paring route mechanism where propene is the predominant product, or side-chain mechanism, with ethene being the predominant product. This finding enables us to establish a relation between the stabilization of the two key intermediates and the experimental selectivity observed with a high degree of correlation. In Chapter 4 we present a new tool for the study of competing reactions catalyzed by zeolites. Using a fast computational screening with force fields for the key intermediates of the reaction and a detailed density functional theory mechanistic study we are able to recognize and quantify subtle differences in the stabilization of intermediates and transition states within similar microporous voids, thus approaching the level of molecular recognition of enzymes. With these tools we are able to select a zeolite catalyst that hinders alkyl-transfer mechanism reducing the production of non-desired ethene while enhancing the diaryl-mediated pathyways mechanism. Once we discard the non-desired mechanism, we are also able to hinder the diethylbenzene disproportionation, a non-desired route of the diaryl-mediated pathways that leads to triethylbenzene production, while favouring diethylbenzene transalkylation increasing the obtained yield of ethylbenzene. To close this chapter, the theoretical results are compared with experimental selectivities obtained for eight candidate zeolites obtaining a good correlation between theory and experiment. in the first section of Chapter 5, we study the energetic affinity of commercially available alkylammonium cations with slight differences on their alkyl chain groups, as TEA, MTEA and DMDEA, for CHA synthesis and its effects on the quality of the material obtained. We evaluate the host-guest interaction energies of different combinations of OSDAs and Na+ cations with periodic DFT methods being able to distinguish small stabilization effects caused by slight structural differences between molecules that have an impact on the final structure synthesized. On the other hand, we present a new theoretical methodology to address Al positioning prediction in SSZ-39 zeolite with the AEI framework. During the second section of Chapter 5, we identify the structural features of different OSDAs for AEI synthesis that improve the probabilities of spreading Al through different T-site positions other than T1 obtaining an AEI catalyst different from the classically synthesized. / Vull agrair al Instituto de Tecnología Química per la concessió d’un contracte predoctoral, a la Red Española de Supercomputación (RES), al Centre de Càlcul de la Universitat de València, al Flemish Supercomputer Center (VSC) de la Ghent University pels recursos computacionals i el suport tècnic, a la Unió Europea i al Gobierno de España pel finançament d’aquest projecte a traves dels programes ERC-AdG-2014- 671093 (SynCatMatch) “Severo Ochoa” (SEV-2016-0683, MINECO) i dels projectes MAT2017-82288-C2-1-P i PID2020-112590GB-C21 (AEI/FEDER, UE), i al CSIC pel finançament de la estada al CMM a través del projecte i- Link (LINKA20381). / Ferri Vicedo, P. (2023). Ab initio design of efficient zeolite catalysts for methanol and hydrocarbons conversion [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/193493