Neste trabalho, foram depositadas sobre lâminas de silício camadas de zeólitos cristalinos, formados por cadeias de átomos de zinco e bases conjugadas do imidazol (ZIF: Zeolitic Imidazolate Framework), com o objetivo de avaliar os processos de adsorção e absorção do CO2 e aplicar essas camadas como pré-concentradores para a detecção de CO2. Para a deposição das camadas ZIF através dos processos Spinning e casting, foi proposta uma solução química alternativa que emprega etanol como solvente em vez de metanol como reportado na literatura, a fim de proporcionar um processo menos tóxico ao ser humano e viabilizar o armazenamento de CO2 para aplicações envolvendo não apenas a sua detecção mas também a sua remoção do ambiente. As camadas ZIF foram depositadas utilizando uma solução obtida a partir da mistura de nitrato de zinco (4,3g) e 2-metilimidazol (9,7g) em etanol com diversas diluições com a finalidade de variar o pH na faixa de 7,2 a 8,2. Como resultado, verificou-se que as camadas obtidas apresentaram estrutura cristalina ZIF-8 ou ZIF-90 apenas na situação de pH próximo de 7. Além disso, as camadas depositadas através da técnica Spinning apresentaram baixa aderência sobre lâminas de silício e não foi possível depositar camadas com espessuras na faixa de micrômetros. Por outro lado, camadas repetitivas com aproximadamente 7, 5µm de espessura foram depositadas nas lâminas de silício através do processo casting em solução de pH = 7,2 (50ml). Após o recozimento dessas camadas na temperatura de 150 ºC por 48h em ambiente de nitrogênio ultrapuro, obtiveram-se distribuições repetitivas de nanocristais com tamanhos na faixa de 5 a 400nm e estrutura cristalina tipo ZIF-90. Das medidas de espectroscopia IR nas camadas de ZIF-90, observou-se que a banda localizada em 2337cm-1 intensifica com o aumento da pressão do CO2 e com o tempo em que a pressão é mantida. Além da banda em 2337cm-1, foi observada uma segunda banda em 2360cm-1, indicando dois diferentes tipos de resposta: (i) a banda em 2337cm-1 foi associada a uma porção substancial de moléculas de CO2 absorvidas dentro da camada junto aos contornos dos nanocristais ou dentro da sua estrutura cristalina, e (ii) a banda em 2360cm-1 foi atribuída à porção de moléculas de CO2 adsorvidas na superfície. Além disso, se o tempo de exposição da camada de ZIF-90 ao CO2, na pressão atmosférica for de pelomenos 2h, atinge-se sensibilidade de 100ppm ao CO2, considerando a leitura mínima de absorbância como sendo igual a 0,02 para 0,5 l/min de CO2 fluindo sobre a amostra. / In this work, layers of crystalline zeolites formed by chains of zinc atoms and conjugate bases of the imidazole (ZIF: zeolitic Imidazolate Framework) were deposited to evaluate the desorption and absorption of CO2 and apply these layers as pre-concentrators for CO2 detection. For the deposition of ZIF layers by means of spinning or casting, it was proposed an alternative chemical solution which employs ethanol as solvent instead of methanol, as reported in the literature, to provide a less toxic process to humans and allow one the CO2 storage applications involving not just detection but also its removal from the environment. The ZIF layers were deposited using a solution prepared from a mixture of zinc nitrate (4.3g) and 2-methylimidazole (9.7g) with several dilutions in ethanol to vary the pH in the range of 7.2 to 8.2. As a result, the crystalline structure of the layers was ZIF-8 or ZIF-90 only for pH next to 7. Furthermore, the layers deposited by spinning showed low adhesion to the silicon wafers and it was not possible to deposit layers for thickness in the micrometer range. Moreover, repetitive layers of approximately 7.5µm in thickness were deposited on the silicon wafers by casting for pH = 7.2 (50ml). After annealing these layers at a temperature of 150 ºC for 48h in ultra-pure nitrogen, it was obtained repetitive nanocrystals with size distributions in the range of 5 to 400 nm having a ZIF-90 crystal structure. From infrared (IR) measurements of the ZIF-90 layers, it was observed a band located at 2337cm-1 that increases with the increase of the CO2 pressure and with the exposure time to this pressure. In addition to the band at 2337cm-1, it was observed a second band at 2360cm-1 indicating two different responses: (i) the band at 2337cm-1 is related to a substantial portion of the CO2 molecules absorbed into the layer along the contours of the nanocrystals or within the crystal structure and (ii) the band at 2360cm-1 is related to the portion of CO2 molecules adsorbed on the surface. Also, if the ZIF-90 layer is exposed to CO2 at atmospheric pressure for at least 2h, a 100ppm sensitivity to CO2 is achieved considering the minimum absorbance as being 0.02 when 0.5 l/min of CO2 is flowing on the sample.

Neste trabalho, foram depositadas sobre lâminas de silício camadas de zeólitos cristalinos, formados por cadeias de átomos de zinco e bases conjugadas do imidazol (ZIF: Zeolitic Imidazolate Framework), com o objetivo de avaliar os processos de adsorção e absorção do CO2 e aplicar essas camadas como pré-concentradores para a detecção de CO2. Para a deposição das camadas ZIF através dos processos Spinning e casting, foi proposta uma solução química alternativa que emprega etanol como solvente em vez de metanol como reportado na literatura, a fim de proporcionar um processo menos tóxico ao ser humano e viabilizar o armazenamento de CO2 para aplicações envolvendo não apenas a sua detecção mas também a sua remoção do ambiente. As camadas ZIF foram depositadas utilizando uma solução obtida a partir da mistura de nitrato de zinco (4,3g) e 2-metilimidazol (9,7g) em etanol com diversas diluições com a finalidade de variar o pH na faixa de 7,2 a 8,2. Como resultado, verificou-se que as camadas obtidas apresentaram estrutura cristalina ZIF-8 ou ZIF-90 apenas na situação de pH próximo de 7. Além disso, as camadas depositadas através da técnica Spinning apresentaram baixa aderência sobre lâminas de silício e não foi possível depositar camadas com espessuras na faixa de micrômetros. Por outro lado, camadas repetitivas com aproximadamente 7, 5µm de espessura foram depositadas nas lâminas de silício através do processo casting em solução de pH = 7,2 (50ml). Após o recozimento dessas camadas na temperatura de 150 ºC por 48h em ambiente de nitrogênio ultrapuro, obtiveram-se distribuições repetitivas de nanocristais com tamanhos na faixa de 5 a 400nm e estrutura cristalina tipo ZIF-90. Das medidas de espectroscopia IR nas camadas de ZIF-90, observou-se que a banda localizada em 2337cm-1 intensifica com o aumento da pressão do CO2 e com o tempo em que a pressão é mantida. Além da banda em 2337cm-1, foi observada uma segunda banda em 2360cm-1, indicando dois diferentes tipos de resposta: (i) a banda em 2337cm-1 foi associada a uma porção substancial de moléculas de CO2 absorvidas dentro da camada junto aos contornos dos nanocristais ou dentro da sua estrutura cristalina, e (ii) a banda em 2360cm-1 foi atribuída à porção de moléculas de CO2 adsorvidas na superfície. Além disso, se o tempo de exposição da camada de ZIF-90 ao CO2, na pressão atmosférica for de pelomenos 2h, atinge-se sensibilidade de 100ppm ao CO2, considerando a leitura mínima de absorbância como sendo igual a 0,02 para 0,5 l/min de CO2 fluindo sobre a amostra. / In this work, layers of crystalline zeolites formed by chains of zinc atoms and conjugate bases of the imidazole (ZIF: zeolitic Imidazolate Framework) were deposited to evaluate the desorption and absorption of CO2 and apply these layers as pre-concentrators for CO2 detection. For the deposition of ZIF layers by means of spinning or casting, it was proposed an alternative chemical solution which employs ethanol as solvent instead of methanol, as reported in the literature, to provide a less toxic process to humans and allow one the CO2 storage applications involving not just detection but also its removal from the environment. The ZIF layers were deposited using a solution prepared from a mixture of zinc nitrate (4.3g) and 2-methylimidazole (9.7g) with several dilutions in ethanol to vary the pH in the range of 7.2 to 8.2. As a result, the crystalline structure of the layers was ZIF-8 or ZIF-90 only for pH next to 7. Furthermore, the layers deposited by spinning showed low adhesion to the silicon wafers and it was not possible to deposit layers for thickness in the micrometer range. Moreover, repetitive layers of approximately 7.5µm in thickness were deposited on the silicon wafers by casting for pH = 7.2 (50ml). After annealing these layers at a temperature of 150 ºC for 48h in ultra-pure nitrogen, it was obtained repetitive nanocrystals with size distributions in the range of 5 to 400 nm having a ZIF-90 crystal structure. From infrared (IR) measurements of the ZIF-90 layers, it was observed a band located at 2337cm-1 that increases with the increase of the CO2 pressure and with the exposure time to this pressure. In addition to the band at 2337cm-1, it was observed a second band at 2360cm-1 indicating two different responses: (i) the band at 2337cm-1 is related to a substantial portion of the CO2 molecules absorbed into the layer along the contours of the nanocrystals or within the crystal structure and (ii) the band at 2360cm-1 is related to the portion of CO2 molecules adsorbed on the surface. Also, if the ZIF-90 layer is exposed to CO2 at atmospheric pressure for at least 2h, a 100ppm sensitivity to CO2 is achieved considering the minimum absorbance as being 0.02 when 0.5 l/min of CO2 is flowing on the sample.

abstract: Membranes are a key part of pervaporation processes, which is generally a more efficient process for selective removal of alcohol from water than distillation. It is necessary that the membranes have high alcohol permeabilities and selectivities. Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71) demonstrated promising alcohol separation abilities. In this dissertation, we present fundamental studies on the synthesis of ZIF-71/PDMS MMMs. Free-standing ZIF-71/ PDMS membranes with 0, 5, 25 and 40 wt % ZIF-71 loadings were prepared and the pervaporation separation for ethanol and 1-butanol from water was measured. ZIF-71/PDMS MMMs were formed through addition cure and condensation cure methods. Addition cure method was not compatible with ZIF-71 resulting in membranes with poor mechanical properties, while the condensation cure method resulted in membranes with good mechanical properties. The 40 wt % ZIF-71 loading PDMS nanocomposite membranes achieved a maximum ethanol/water selectivity of 0.81 ± 0.04 selectivity and maximum 1-butnaol/water selectivity of 5.64 ± 0.15. The effects of synthesis time, temperature, and reactant ratio on ZIF-71 particle size and the effect of particle size on membrane performance were studied. Temperature had the greatest effect on ZIF-71 particle size as the synthesis temperature varied from - 20 to 35 ºC. The ZIF-71 synthesized had particle diameters ranging from 150 nm to 1 μm. ZIF-71 particle size is critical in ZIF-71/PDMS composite membrane performance for alcohol removal from water through pervaporation. The membranes made with micron sized ZIF-71 particles showed higher alcohol/water selectivity than those with smaller particles. Both alcohol and water permeability increased when larger sized ZIF- 71 particles were incorporated. ZIF-71 particles were modified with four ligands through solvent assisted linker exchange (SALE) method: benzimidazole (BIM), 5-methylbenzimidazole (MBIM), 5,6- dimethylbenzimidazole (DMBIM) and 4-Phenylimidazole (PI). The morphology of ZIF- 71 were maintained after the modification. ZIF-71/PDMS composite membranes with 25 wt% loading modified ZIF-71 particles were made for alcohol/water separation. Better particle dispersion in PDMS polymer matrix was observed with the ligand modified ZIFs. For both ethanol/water and 1-butanol/water separations, the alcohol permeability and alcohol/water selectivity were lowered after the ZIF-71 ligand exchange reaction. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2017

Les réseaux zéolithiques à base d'imidazolate (e.g. ZIF-8) sont des matériaux membranaires attractifs pour la séparation de gaz, sous réserve de pouvoir disposer de membranes de haute qualité, stables et reproductibles sur des supports industriels. Dans ce travail plusieurs stratégies ont été examinées pour développer des membranes nanocomposites à base de ZIF-8 confiné dans les macropores de supports céramiques tubulaires. Trois approches ont été comparées: i) croissance de germes, ii) croissance in situ et iii) conversion de ZnO. L'influence des paramètres de synthèse (formulation des solutions de précurseurs, température & durée de réaction, type de support & prétraitement…) sur les caractéristiques et performances des membranes a été étudiée. Le protocole optimum retenu repose sur la conversion solvothermale de couches minces de ZnO déposées par ALD sur les grains du support. Les membranes nanocomposites ZIF-8/ZnO/α-Al2O3 sont sélectives pour la séparation de gaz contenant H2. / Zeolitic Imidazolate Frameworks (e.g. ZIF-8) are attractive membrane materials for gas separation, provided that high quality, stable and reproducible membranes can be prepared on industrial supports. In this work several strategies were investigated in order to develop nanocomposite ZIF-8 based membranes confined in the macropores of tubular ceramic supports. Three approaches were compared: i) seeded growth, ii) in situ growth and iii) ZnO conversion. The influence of synthesis parameters (precursor solution formulation, reaction temperature & duration, support type & pre-treatment…) on membrane characteristics and performance were studied. The selected optimum protocol was based on the solvothermal conversion, using a 2-methylimidazole/methanol solution, of a ZnO thin layer uniformly deposited by Atomic Layer Deposition on the grains of a ceramic support. The nanocomposite ZIF-8/ZnO/α-Al2O3 membranes exhibited enhanced selectivities for the separation of H2-containing gas mixtures.

In the last decade, many attempts were made to put metal organic frameworks (MOFs) in industrial applications, but most of these efforts weren’t successfully. As one of the few MOFs produced on industrial scale, ZIF-8 has interesting pore size, huge internal surface area and great thermal and chemical stability. Therefore, ZIF-8 might become the first MOF, which will be applied in industrial separation processes. In this thesis, a synthesis study is presented, which leads to a cheap and convenient way to
fabricate defect-free and thin ZIF-8 membranes on porous polymeric supports showing high selectivity and high gas permeance. The ZIF-8 layers were produced via a contra-diffusion method. Several polymeric membranes were employed as support in this study, such as PAN, PEI, PSU, PA and PTSC. We studied the influence of the polymeric support properties for the ZIF-8 membrane preparation and optimized the ZIF-8 preparation conditions. The ZIF-8 membranes were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD). For gas permeation test, we chose a Wicke-Kallenbach apparatus to measure membrane’s gas permeance and selectivity. One of the best ZIF-8 membranes exhibited a hydrogen permeance of 3.45 × 10-8 mol m-2 s-1 Pa-1 and
an ideal selectivity of hydrogen over propane of about 500.

El 25 de septiembre de 2015, la Organización de las Naciones Unidas, mediante el Acuerdo de París, adoptó 17 objetivos globales para asegurar la prosperidad y el bienestar global futuros. Entre estos objetivos, destaca el número 13 “Acción por el clima”, en el que dicha organización pide encarecidamente la disminución y reducción de las emisiones de CO2 como principal gas portador del efecto invernadero. Esta tesis doctoral se encuentra incluida en dicho marco, a través del cual se han desarrollado una serie de materiales híbridos que han sido utilizados como catalizadores en una reacción para secuestrar CO2 y valorizarlo. Los Metal-Organic Frameworks (MOF) se caracterizan por su gran porosidad y surgen a partir de la combinación de compuestos orgánicos e inorgánicos dentro de una estructura cristalina. Estos materiales híbridos poseen poros bien definidos y muy accesibles, haciéndolos atractivos en un amplio rango de aplicaciones. Esta característica, así como su alta estabilidad térmica y su moderada estabilidad química, los hacen ser unos candidatos potenciales para ser utilizados como catalizadores heterogéneos. Sin embargo, no todos los MOF exhiben dichas cualidades o muestran buena conductividad eléctrica o de fácil manipulación para ser usados como catalizadores. Por esta razón, en esta tesis doctoral se han desarrollado nuevas vías de síntesis de MOF a partir de sustratos metálicos que abren nuevas oportunidades a crear MOF de una manera eficiente y viable para la industria. Asimismo, también se ha llevado a cabo un procedimiento innovador de inducción de defectos en los MOF de forma post-sintética con el objetivo de mejorar las propiedades catalíticas de estos. Los materiales que hemos preparado en esta tesis han sido probados como catalizadores heterogénos bifuncionales en la reacción de cicloadición de CO2 con epiclorhidrina. Se trata de una reacción que no involucra la reducción del átomo del carbono en el CO2, sino que se trata de una fijación del CO2 por parte del epóxido, lo que implica un aporte mucho menor de energía. En esta tesis doctoral se ha observado que la inducción de defectos en la estructura del MOF trae consigo una mejora en la actividad catalítica en la reacción. Además, también se ha estudiado que una distinta morfología de los cristales de MOF y una diferente distribución de planos presentes en la superficie externa del mismo también afecta significativamente a la estabilidad del cristal. Por último, cabe destacar que, a pesar de lo que se advierte en la bibliografía, el ZIF-67, uno de los MOF más utilizados como catalizador en la cicloadición de CO2 con epiclorhidina, no es tan estable en la reacción. Se observó que la estabilidad de dicho MOF está influida por la cantidad de planos expuestos {100}, que son altamente inestables en las condiciones de la reacción y son los causantes del lixiviado de cobalto y especies orgánicas que cataliza verdaderamente la reacción.

Les travaux de cette thèse concernent la compréhension à l'échelle atomique des processus physico chimiques intervenant aux interfaces et dans des phases diluées. Pour commencer, nous avons étudié l'interaction entre la molécule 1,4-diazabicyclo [2.2.2]octane (DABCO) et un atome de gaz rare (He, Ne, Ar, Kr). Nous avons effectué une analyse systématique de ces systèmes, et nous en avons conclu que la méthode MP2 associée à une base diffuse est suffisamment précise pour décrire le système DABCO – Ar. Les surfaces d'énergie potentielle des complexes DABCO – gaz rare ont été calculées, ce qui nous a permis de réattribuer les spectres expérimentaux de ces espèces. Ensuite, nous nous sommes concentré sur les complexes DABCO – Arn (avec n = 2, 3, 4) neutres et ioniques. Nous avons montré que le DABCO interagi avec les atomes d'argon, et subit des déformations dues à l'effet de cette interaction faible sur ses modes de vibration. Par la suite, nous avons étudié les plus bas états électroniques du DABCO – Arn (n = 1, 2, 3). Nos résultats pourront être étendus à l'interprétation qualitative des études spectroscopiques et dynamiques des molécules de DABCO absorbés dans de grands agrégats d'argon. Enfin, nous avons étudié l'interaction entre l'imidazole et une couche d'or en présence de CO2. Nous avons montré que la molécule d'imidazole se fixe à l'agrégat d'or par une liaison covalente entre l'atome d'azote et un atome d'or, ainsi que des interactions faibles de type van der Waals entre les atomes d'hydrogène et la surface d'or. Nous avons déterminé que le site préférentiel pour l'interaction imidazole – or est le site top. Cette interaction permet un transfert de charge de l'imidazole vers la surface d'or, ce qui affecte la capture du CO2 (environ 50% plus faible par rapport à l'interaction Im(seule) – CO2). Mais l'augmentation du nombre de molécules d'imidazole à la surface de la couche d'or pourrait permettre une liaison plus forte entre le CO2 et l'imidazole / This thesis concern the understanding at the atomic level of physicochemical processes occurring at interfaces and dilute phases. First, we studied the interaction between the 1,4- diazabicyclo [2.2.2] octane (DABCO) molecule and a rare gas atom (He, Ne, Ar, Kr). We conducted a systematic analysis of these complexes, and we concluded that the MP2 method with a diffuse basis set is accurate to describe the system DABCO – Ar. The potential energy surfaces of DABCO – rare gas complexes were calculated, which allowed us to reatribuate the experimental spectra of these species. Then, we focused on DABCO – Arn (n = 2, 3, 4) neutral and ionic clusters. We have shown that the DABCO interacted with argon atoms and undergoes deformation due to the effect of the weak interaction on his vibrational modes. Subsequently, we studied the lowest electronic states of DABCO – Arn (n = 1, 2, 3). Our results can be extended to the qualitative interpretation of spectroscopic and dynamic studies of absorbed DABCO in large argon clusters. Finally, we studied the interaction between imidazole and a gold surface with CO2. We have shown that the imidazole molecule binds to the gold surface by a covalent bond between the nitrogen atom and a gold atom, and van der Waals interactions between hydrogen atoms and the gold surface. We determined that the preferred site for the imidazole – gold interaction is the top site. This interaction allows a charge transfer from the imidazole to the gold surface, which affects the capture of CO2 (about 50% lower compared to the interaction Im – CO2). But increase number of imidazole molecules on the gold surface could lead to a stronger bond between CO2 and imidazole

Depuis plusieurs années, les MOFs (Metal Organic Frameworks) suscitent une grande attention pour leurs applications potentielles en catalyse hétérogène. Ces matériaux sont également étudiés dans les domaines de la séparation, du stockage de gaz, de la libération contrôlée ou comme systèmes de vectorisation de médicaments. Leur structure complexe étant formée par des centres de coordination métalliques unis par des ligands polydentates, les MOFs disposent de nombreux sites acido-basiques de Lewis ou de Brönsted qui sont cruciaux pour l'activité des matériaux et la sélectivité des produits lors des réactions catalysées par les MOFs. Dans ce travail, nous nous sommes tout particulièrement intéressés à une classe de MOFs appelée « zéolithic imidazolate frameworks » (ZIF-8). Les ZIF-8 présentent de nombreuses propriétés intéressantes, notamment une grande surface spécifique, une faible densité, une forte porosité ainsi qu’une excellente stabilité chimique et thermique. Dans une première partie, la préparation de matériaux ZIF-8 et d’hétérostructures à base ZIF-8 a été développée afin de conférer à ces matériaux des propriétés adaptées à l'application souhaitée. La mise en forme de ces catalyseurs a également été étudiée afin d’obtenir la forme optimale pour une utilisation industrielle de ces matériaux. En variant le précurseur d’ions Zn2+ utilisé pour la synthèse, nous avons démontré que les propriétés (taille, porosité, ...) de ZIF-8 cristaux pouvaient être contrôlées en fonction de l’application catalytique recherchée. Ces ZIF-8 cristaux ont été utilisés avec succès en tant que catalyseurs hétérogènes dans les réactions de Knoevenagel et Friedländer. Nous avons développé de nouveaux matériaux ZIF-8 dopés par des ions Cu2+. Les particules Cu/ZIF-8 se sont montrés être des catalyseurs efficaces dans la réaction de Combes et la cycloaddition de Huisgen. La recyclabilité du matériau a été évaluée et il a notamment été montré que les particules ZIF-8 pouvaient être réutilisées jusqu'à dix fois sans perte d'activité catalytique. Nous avons également fonctionnalisé les cristaux ZIF-8 avec des particules magnétiques Fe3O4. L’hétérostructure hybride Fe3O4@ZIF-8 peut facilement être récupérée par séparation magnétique après les expériences de catalyse. Afin d’étendre le champ d’application des catalyseurs ZIF-8, le matériau a également utilisé pour la conversion du dioxyde de carbone en carbonates cycliques en utilisant un réacteur du Parr. Comme la réaction est d’un grand intérêt industriel, le catalyseur a été mis en forme par compression. Dans la dernière partie de ce mémoire, la toxicité des particules ZIF-8 et ZIF-8 dopé par Cu ou Fe a été évaluée en utilisant des cellules alvéolaires A549 et de la peau IHK comme modèles. La stabilité des particules a été déterminée à l’aide de milieux mimant la digestion des particules in vivo. Les résultats obtenus montrent que les particules sont très sensibles aux variations de pH ainsi qu’aux sels présents dans les différents milieux / Metal organic frameworks (MOFs) have gained considerable attention as heterogeneous catalytic systems and also have been studied in the area of separation, gas storage, controlled release or as drug delivery systems. According to their complex structure formed by metal centers coordinated with polydentate linkers, MOFs expose abundance of Lewis and/or Brönsted acid-base sites that are crucial for the materials catalytic activity and selectivity towards specific reactions. Moreover, these materials have many other attractive properties, including a large surface area, a low density and a high porosity. In this work, we focused on the zeolithic imidazolate framework (ZIF-8) material – a MOF exhibiting high porosity and stability and which can also be used as a template for further functionalization and modification. Firstly, we focused on the preparation of ZIF-8 crystals and ZIF-8 heterostructures with properties adapted to the desired application, and then shaping of the catalyst to obtain the best form of material for industrial scale-up utilization. By varying Zn2+ precursors used for the synthesis, we demonstrated that the properties (size, porosity,…) of ZIF-8 crystals can be controlled and tuned depending on the applications. These ZIF-8 crystals were successfully applied as heterogeneous catalysts in Knoevenagel and Friedländer reactions. Next, we developed protocols for the synthesis of Cu2+-doped ZIF-8 crystals. The use of these crystals could be extended to Cu-mediated reactions, like the Combes condensation and the Huisgen cycloaddition. We evaluated recyclability and we showed that the nanomaterials could be reused up to ten times without any loss of catalytic activity. Moreover, we functionalized ZIF-8 crystals with magnetic Fe3O4 nanoparticles. The hybrid Fe3O4@ZIF-8 heterostructures could be easily recovered by magnetic separation after catalytic experiments. To show multiple benefits originating from the ZIF-8 structure and properties, we also used this material for the conversion of CO2 into cyclic carbonates using a Parr reactor. As the reaction could be scale-up at the industrial level, we shaped the powder in the form of pellets and use it under the same conditions. In the last chapter, we evaluated the toxicity and the stability in biological media of ZIF-8, Cu- and Fe-doped ZIF-8 particles using A549 alveolar cells, IHK skin cells as models and in vitro ingestion under fed conditions. These models were chosen according to the most probable first contact entering gates for nanoparticles inside human body, skin, lungs and digestive tract. Outcomes from these preliminary studies motivated us to conduct extended stability tests of the particles in different media. We showed that the particles are altered by pH changes and medium complexity

This master’s thesis was conducted at the Department of Nanotechnology and Functional Materials at Ångström Laboratory as part of an on-going project to develop hybrid nanocomposites from Cladophora cellulose and a sub-type of metal-organic frameworks; zeolitic imidazolate frameworks (ZIFs). By utilizing a state-of-the-art interfacial synthesis approach, in-situ growth of ZIF particles on the cellulose could be achieved. TEMPO-mediated oxidation was diligently used to achieve cellulose nanofibers with carboxylate groups on their surfaces. These were ion-exchanged to promote growth of ZIF particles in a nanocellulose solution and lastly, metal ions and organic linkers which the ZIFs are composed of were added to the surface functionalized and ion-exchanged nanocellulose solution to promote ZIF growth. By vacuum filtration, mechanical pressing and furnace drying; freestanding nanopapers were obtained. A core-shell morphology between the nanocellulose and ZIF crystals was desired and by adjusting the metal ion concentration, a change in morphologies was expected. The nanocomposites were investigated with several relevant analytical tools to confirm presence, attachment and in-situ growth of ZIF crystal particles upon the surface of the fine nanocellulose fibers. Both the CNF@ZIF-67 and CNF@ZIF-8 nanocomposites were successfully prepared as nanopapers with superior surface areas and thermal properties compared to pure TEMPO-oxidized cellulose nanopapers. The CNF@ZIFs showcased hierarchical porosities, stemming from the micro- and mesoporous ZIFs and nanocellulose, respectively. Also, it was demonstrated that CNF@ZIF-8 selectively adsorbed CO2 over N2. Partial formation of core-shell structure could be obtained, although a relationship between increased metal ions and ZIF particle morphology could not wholly be observed.

Thesis advisor: Chia-Kuang (Frank) Tsung / Exchange reactions have enabled a new level of control in the rational, stepwise preparation of metal-organic framework (MOF) materials. However, their full potential is limited by a lack of understanding of the molecular mechanisms by which they occur. This dissertation describes our efforts to understand this important class of reactions in two parts. The first reports our use of a linker exchange process to encapsulate guest molecules larger than the limiting pore aperture of the MOF. The concept is demonstrated, along with evidence for guest encapsulation and its relation to a dissociative linker exchange process. The second part describes our development of the first quantitative kinetic method for studying MOF linker exchange reactions and our application of this method to understand the solvent dependence of the reaction of ZIF-8 with imidazole. This project involved the collection of the largest set of rate data available on any MOF linker exchange reaction. The combination of this dataset with small molecule encapsulation experiments allowed us to formulate a mechanistic model that could account for all the observed kinetic and structural data. By comparison with the kinetic behavior of complexes in solution, we were able to fit the kinetic behavior of ZIF-8 into the broader family of coordination compounds. Aside from the specific use that our kinetic data may have in predicting the reactivity of ZIF linker exchange, we hope that the conceptual bridges made between MOFs and related metal−organic compounds can help reveal underlying patterns in behavior and advance the field. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.