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

Les enzymes sont des biocatalyseurs de plus en plus utilisés pour la transformation de molécules organiques (chimie fine, bioconversions, dépollution, chimie du pétrole) car elles possèdent de très bonnes sélectivité et réactivité, générant rapidement de larges quantités de produit. Cependant, la fragilité des enzymes, notamment en solution, limite souvent leur utilisation. Il est donc crucial de les immobiliser et de les stabiliser dans des supports adaptés. Une grande variété de matrices d’immobilisation (organiques ou inorganiques) a déjà étudiée, mais aucune ne satisfait pleinement aux critères nécessaires pour le développement de bio-réacteurs (accessibilité au site actif de l’enzyme, relargage de l’enzyme, diffusion des réactifs, recyclabilité, stabilité..). En outre, la majorité de ces matrices présente une porosité désordonnée, inadaptée pour une immobilisation homogène. L’utilisation de matériaux hybrides, cristallins et poreux de type Metal-Organic Frameworks (MOFs) a été récemment proposée comme alternative avec des applications en biocatalyse et en biodétection.Le travail de cette thèse a consisté à associer des matériaux de type Metal-Organic Frameworks à une mini-enzyme, la microperoxidase 8 (MP8), afin d’obtenir des matériaux multifonctionnels. Dans une première partie, le MOF mésoporeux, MIL-101(Cr), a été utilisé pour encapsuler la MP8, ce qui a conduit à une amélioration de son activité catalytique dans des conditions qui ne sont pas adéquates pour l’activité enzymatique (conditions acides, forte concentration en H2O2), démontrant ainsi le rôle protecteur du MOF vis-à-vis de l’enzyme. De plus, il a été possible de recycler le biocatalyseur. Cette approche a également permis d’améliorer considérablement la sélectivité de la MP8 pour la dégradation d’un colorant organique toxique négativement chargé, le méthyl orange, grâce à son adsorption sélective par interaction électrostatique avec les particules de MIL-101(Cr). La seconde partie a été consacrée à l’utilisation de matériaux MIL-101(Cr) fonctionnalisés. Tout d’abord, l’influence de la fonctionnalisation du ligand (avec un groupement –NH2 ou –SO3H) sur l’encapsulation de la MP8 ainsi que sur son activité catalytique pour des réactions de sulfoxydation a été étudiée. Il a été montré que l’activité catalytique et la réactivité de la MP8 sont affectées par le microenvironnement spécifique des pores du MOF, notamment pour des réactions de sulfoxydation mettant en jeu des dérivés thioanisole. Ensuite, un MOF à métal mixte (MIL-101(Cr/Fe)) choisi pour ses propriétés catalytiques stables, a été synthétisé et caractérisé. Enfin, la dernière partie de cette thèse a été consacrée à la synthèse in-situ d’un MOF (le microporeux MIL-53(Al)-FA) en présence de biomolécules (BSA) dans des conditions compatibles avec la préservation de la structure protéique (en solution aqueuse à température ambiante). Les matériaux hybrides obtenus ont été caractérisés en couplant de nombreuses techniques. Cette méthode d’encapsulation a conduit à des taux d’immobilisation extrêmement élevés. Une étude préliminaire a été initiée avec l’enzyme, Horseradish Peroxidase , qui conserve son activité catalytique après immobilisation. / The use of enzymes in biocatalytic processes has been a challenging goal over the years. While enzymes present exceptional catalytic properties, their fragility hinders their industrial application. Their stabilization and protection are therefore of paramount importance. This can be effectively addressed through their immobilization within host solid matrices. Traditional materials (silica, clays, polymers, biopolymers, porous carbons…) have been widely studied as supports. Their pure organic or inorganic nature often requires a compromise between affinity with enzymes and robustness of the matrix. Besides, most of them have non-ordered porosity, with non-homogenous pore size distributions, unsuitable for homogeneous immobilization. Metal-Organic Frameworks (MOFs) have been recently introduced as alternative supports, thanks to their hybrid nature and their crystalline and highly porous structures.The aim of this PhD was to combine Metal-Organic Frameworks (highly porous and chemically stable polycarboxylate MOFs) and a mini-enzyme, microperoxidase 8 (MP8) to obtain multifunctional biocatalysts. In a first part, the mesoporous MIL-101(Cr) was used as a host matrix to encapsulate MP8. The encapsulation led to an increased catalytic activity under conditions (acidic conditions, high concentration of H2O2) detrimental to the catalytic activity of MP8, thereby demonstrating the protecting effect of MIL-101(Cr) matrix. The biocatalyst was also efficiently recycled. The selectivity of MP8 for the degradation of the harmful negatively charged organic dye methyl orange was also enhanced, thanks to the charged-based selective adsorption of the dye in MIL-101(Cr) porosity. A second part of the work was devoted to the use of functionalized MIL-101(Cr) analogs. First, functionalized ligands (bearing –NH2 and –SO3H groups) were used, and their influence on MP8 encapsulation was evaluated. The catalytic activity toward sulfoxidation reactions was also studied. The successful encapsulation of MP8 was strongly dependent on charge matching between the enzyme and the MOFs particles, while its catalytic activity was affected by the specific microenvironment of the pores. The MOF frameworks also modified the reactivity of MP8 toward different thioanisole derivatives. Then, a mixed metal MOF (MIL-101(Cr/Fe)), selected for its stable catalytic properties, was synthesized and characterized. Finally, the last part was devoted to the in-situ synthesis of MOFs (microporous MIL-53(Al)-FA) in presence of biomolecules (BSA) under compatible conditions with the preservation of the protein’s quaternary structure (aqueous media and room temperature). The resulting hybrid materials were thoroughly characterized and presented high loadings of BSA. A preliminarily study was performed with the enzyme, Horseradish Peroxidase, which retained its catalytic activity after immobilization.

The main goal of this work is to search for new stable porous carbon-based materials, which have the ability to accommodate and store hydrogen gas. Theoretical and experimental studies suggest a close relation between the nano-scale structure of the material and its storage capacity. In order to design materials with a high storage capacity, a compromise between the size and the shape of the nanopores must be considered. Therefore, a number of different carbon-based materials have been investigated: carbon foams, dislocated graphite, graphite intercalated by C60 molecules, and metal-organic frameworks. The structures of interest include experimentally well-known as well as hypothetical systems. The studies were focused on the determination of important properties and special features, which may result in high storage capacities. Although the variety of possible pure carbon structures and metal-organic frameworks is almost infinite, the materials described in this work possess the main structural characteristics, which are important for gas storage.

Les MOFs sont des matériaux hybrides (organiques/inorganiques), nanoporeux et cristallin. La périodicité et la porosité apportent à ces matériaux des propriétés modulables par la topologie des réseaux et par les interactions entre le réseau et les molécules qui peuvent pénétrer dans les nanopores. L'adsorption de molécules dans les pores permet les séparations de mélanges, la séquestration sélective de molécules, la catalyse, le stockage de l'énergie etc... La flexibilité de certains MOFs est caractérisée par des variations de volume, parfois extrêmes, pouvant modifier de manières significatives les propriétés de ces matériaux. L'eau est tout à la fois une impureté inévitable dans les usages pratiques de ces composés mais également un composant important dans la modulation de la flexibilité. Bien que les nombreuses études publiées offrent une vision globale de la flexibilité et des interactions mises en jeu lors de l'adsorption de molécules de différentes natures, l'eau reste cependant une de celles qui résistent le plus aux mesures et aux interprétations. Cette thèse a eu pour objet d'utiliser de façon conjointe la diffraction des rayons-X synchrotron, des neutrons et a résonance magnétique nucléaire (RMN), pour ré-investiguer le rôle de l'eau dans la flexibilité de deux MOFs archétypiques, le UiO-66 (ZrCDC) et le MIL-53(Al). Nos résultats ont permis d'éclairer plusieurs points critiques. Avec ZrCDC il a pu être montré qu'en présence d'eau, les deux briques de constructions, inorganique et organique, sont couplées tout en ayant chacune une flexibilité distincte. Pour MIL-53(Al), la réinvestigation a été notablement plus conséquente, reprenant le suivi de la flexibilité en température de la phase anhydre et sous l'influence des gaz composants de l'air, oxygène et azote, puis l’étude du rôle de l'eau par RMN qui permet de caractériser les modifications structurales et dynamiques des phases anhydre et hydratée. Le suivi progressif de l'adsorption et de la désorption a notamment permis de mettre en évidence des phénomènes d'échange protoniques lents responsables des hystérèses observés. Ces résultats permettent de remettre en perspective les études antécédentes et de proposer une description renouvelée de la flexibilité de ces composés, comme une "horlogerie cristalline" des mouvements moléculaires. / MOFs (metal-organic-frameworks) are hybrid (organic/inorganic) crystalline nanoporous materials. Periodicity and porosity provide to these materials modularity of properties by the topology of networks, and interactions between the framework and penetrating molecules in nanopores. Adsorption of molecules in pores allows for mixtures separation, selective sequestration of molecules, catalysis, storage of energy etc... Flexibility of some MOFs is characterized by extremes volume variations modifying properties of these materials. Water is at the same time an inevitable impurity in practical uses of such compounds and an equally significant component for modulation of flexibility. Although many published studies provide comprehensive views of the flexibility and interactions involved in the adsorption of molecules of different types, however water is one of those most resistant to measurements and interpretations. This thesis has been using jointly X-rays synchrotron and neutrons diffractions as well as nuclear magnetic resonance, to re-investigate water role on two archetypical MOFs, UiO-66 (ZrCDC) and MIL-53(Al). Our results obtained along this thesis shed some light on several critical points. With ZrCDC it has been demonstrated that both building blocks, inorganic and organic, exhibit each of them, in the presence of water a distinct flexibility, coupled together. For MIL-53(Al), this reinvestigation was noticeably more studied, covering flexibility in temperature of the anhydrous phase and under the influence of the components of air, oxygen and nitrogen. Then the study of water role in the anhydrous and hydrated phase by NMR characterized structural and dynamic changes. A progressive monitoring of adsorption and desorption, brought out slow proton exchange phenomena responsible of the hysteresis. These results allow for redefined a perspective of previous investigations and to propose a renewed description of flexibility of these materials, as a "crystalline clockwork" of molecular motions.

The research work reported in this dissertation is focused on exploring the systematic syntheses and characteristics of lanthanide-containing functional materials. Lanthanides have interesting properties that arise as a consequence of f-electrons, namely, magnetism, luminescence, and flexible coordination sphere. These studies were extended further into heterometallic systems containing transition metal ions, specifically Ni(II) and Co(II), to further explore the behavior of lanthanides in functional materials with addition of transition metal ions. The results include the high nucleraity lanthanide hydroxide clusters and metal-organic frameworks which showed potential applications in catalysis, separations, solid-state light-emitting devices and magnetism. Chapter 1 provides background on lanthanides and different types of lanthanide-containing materials, their properties, and potential applications followed by a synopsis to the research work in each chapter. In Chapter 2, the synthesis, structure characterization, magnetic studies and solution stability studies of a novel class of high-nuclearity lanthanide hydroxide cluster complexes {Ln54} with Chromogen I, a ligand transformed from in situ N-Acetyl-D-glucosamine are summarized. Attention is focused on this ligand transformation since it shows a possible pathway for selective and efficient transformation of biomass into useful chemicals with the unique coordination chemistry of lanthanides. The remainder of this chapter is focused on using hydroxylcarboxylic acids for the formation of high-nuclearity lanthanide hydroxide clusters with the aim of expanding the array of ligands that can be utilized for developing these systems. Chapter 3 discusses the synthesis, structural characterization and photoluminescence properties of a novel series of lanthanide metal-organic frameworks utilizing iminodiacetic acid as bridging ligand. The possibility of luminescence color tuning employing mixed metal system containing Eu and Tb was shown. The lifetimes for the luminescence systems were evaluated based on photo decay studies in order to understand the energy transfer processes in the mixed-metal system. An energy transfer from Tb to Eu was evident based on the data. Chapter 4 focuses on a 3d-4f heterometallic system based on Ni(II) that has been synthesized using a metalloligand approach. A metalloligand containing Ni was first synthesized and then used for further lanthanide coordination. The result of this effort was a bi-porous metal-organic framework (MOF) which contains both hydrophilic and hydrophobic pores. The magnetic studies showed weak antiferromagnetic interactions between the Ni centers and confirmed the absence of single-molecule magnet behavior. Chapter 5 explores another 3d-4f heterometallic system which contains Co(II) using a different synthetic approach than that reported in Chapter 4. A 2-D layer type MOF containing both Ln(III) (Ln= Pr, La, Nd) Co(II) was obtained with the use of iminodiacetic acid as the supporting ligand under solvothermal conditions which further extends to a 3-D network with extensive hydrogen bonding. Magnetic studies were carried out to explore the magnetic interactions between the metal ions and results were not conclusive due to the complicated intrinsic magnetic characteristics possessed by both Ln(III) and Co(II).Chapter 6 describes results on another lanthanide-containing MOF that assembles as a layered material creating channels between the layers. The structural analysis of the MOF of interest and other MOFs obtained under the controlled conditions were discussed. This work has potential applications as an advanced material for proton conductivity, intercalation, and ion exchange. Chapter 7 summarizes the body of work by examining the results and significance of the results presented in Chapters 2-6 and discusses the future directions possible for each project. Appendix A provides all the crystallographic information including bond lengths and angles.

This thesis is built upon two areas of research concerning metal-organic frameworks (MOFs). The first focuses on the functionalisation of MOFs via post-synthetic modification (PSM). The second involves the investigation on the potential of MOFs as hosts for insect pheromones. Chapter 1 introduces the field of MOF chemistry, and covers their properties along with a brief description of their applications. The concept of PSM is introduced and a review of recent literature given. The aims of the thesis are also detailed at the end of this chapter. Chapter 2 describes the PSM of [Zr6O4(OH)4(BDC-NH2)6], UiO-66-NH2, via Aza-Michael reactions. Different functionalities were successfully introduced into its pores and the degrees of conversion were determined via 1H NMR spectroscopy. Gas sorption measurements (CO2 and N2) of the PSM products were carried out and compared. In particular, two PSM products were shown to exhibit higher CO2 over N2 selectivity than that for the starting MOF, UiO-66-NH2. Chapter 3 describes a new PSM route in obtaining azole-functionalised MOFs via Mannich reactions. The amino groups in three different MOFs were converted into a range of azole-functionalised MOFs with conversions up to 100%. In particular, one of the PSM reactions afforded a new material, formulated as [Zn3(BDC-NH2)1.32(BDC-NHCH2N2C3H3)1.68(C6H12N2)], based on single crystal X-ray crystallography, 1H NMR and TGA analyses. Gas sorption studies demonstrate increased selectivity for CO2 over N2 for the PSM products. One of the modified MOFs was shown to exhibit a high Hg(II) uptake from aqueous solutions. Chapter 4 introduces the concept of using MOFs as hosts for ant pheromones. The factors which influenced the pheromone loading in zinc and zirconium based MOFs were investigated. The MOFs containing the linker BDC-NHPr (2-(propylamino)benzene-1,4-dicarboxylate) were found to be effective at hosting two types of ant pheromones, 3-octanone and (S)-4-methyl-3-heptanone.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O gÃs natural, cuja maior parte à constituÃda de metano, à um combustÃvel que vem se expandindo no mercado energÃtico global por possuir uma queima mais limpa que outros derivados petrolÃferos e por ser mais eficiente energeticamente. No entanto, ele possui como grande desvantagem frente a outros combustÃveis a dificuldade em ser armazenado devido a sua baixa densidade. Materiais microporosos vÃm sendo utilizados para aumentar tal densidade por meio da adsorÃÃo. No entanto, um dos problemas encontrados na utilizaÃÃo desses materiais se trata da diminuiÃÃo da capacidade adsortiva apÃs ciclos de carga e descarga de tanques de armazenamento. O estudo desse problema, porÃm, demanda um grande nÃmero de experimentos e uma aparelhagem relativamente sofisticada. Este trabalho propÃs a simulaÃÃo molecular como uma metodologia vÃlida a ser utilizada para o estudo da retenÃÃo de alcanos em carbono ativado e em oito estruturas metalorgÃnicas: IRMOF-1, ZIF-8, CuBTC, PCN-11, PCN-14, UiO-66, MIL-100 e MIL-101. Considerou-se o gÃs natural como uma mistura de metano (C1), etano (C2), propano (C3) e butano (C4) nas proporÃÃes de, respectivamente, 84,7:10:0,9:0,1. Para a validaÃÃo dos modelos utilizados nassimulaÃÃes, as isotermas simuladas de C1, C2, C3 e C4 foram ajustadas Ãs experimentais obtidas da literatura para cada um dos materiais. Foram entÃo realizadas isotermas multicomponentes e estudo de sÃtios de adsorÃÃo para o estudo da retenÃÃo de hidrocarbonetos e da influÃncia de fatores composicionais e estruturais nesse fenÃmeno. Observou-se que as MOFs MIL-100 e ZIF-8 sÃo as mais recomendadas para uso em tanques de GNA por critÃrios de capacidade, eficiÃncia adsortiva e estabilidade. Verificou-se ainda que MOFs que apresentam sÃtios de adsorÃÃo pouco dispersos apresentam uma maior tendÃncia à acumulaÃÃo de hidrocarbonetos. / Natural gas, which consists mostly of methane, is a fuel that has been expanding in the global energy market by having a cleaner burning than other petroleum derivatives and are more energy efficient. However, it has a great disadvantage compared to other fuels: it is difficult to be stored due to its low energy density. Microporous materials have been used to increase the energy density by adsorption. However, one of the problems encountered in using these materials it comes to the decrease in adsorption capacity after charge and discharge cycles of the storage tanks. The study of this problem, however, requires a large number of experiments and a relatively sophisticated equipment. This paper proposes themolecular simulation as a valid methodology to study the retention of alkanes in activated carbon, and eight metalorganic structures: IRMOF - 1, ZIF - 8, CuBTC, PCN- 11, PCN -14, UiO -66, MIL -100 and MIL- 101. We considered the natural gas as a mixture of methane (C1), ethane (C2), propane (C3) and butane (C4) in the proportions respectively 84,7:10:0,9:0,1. For the validation of the models used in the simulations, the simulated isotherms of C1, C2, C3 and C4 were adjusted to fit the experimental ones, obtained from the literature data for every material. Multicomponent isotherms were then performed, the retention of hydrocarbons were studied as well as the influence of compositional and structural factors to this phenomenon. We noticed that the MOFs MIL-100 and ZIF-8 are the most recommended to use in GNA tanks according to the criteria of capacity, adsorption efficiency and stability. We verified as well that MOFs that have adsorption sites too localized present a larger tendency to the accumulation of hydrocarbons.

Tese de Mestrado Integrado. Engenharia Química. Faculdade de Engenharia. Universidade do Porto. 2012

Global climate change is one of the most challenging problems that human beings are facing. The large anthropogenic emission of CO2 in the atmosphere is one of the major causes for the climate change. Coal-fired power plants are the single-largest anthropogenic emission sources globally, accounting for approximately one third of the total CO2 emissions. It is therefore necessary to reduce CO2 emission from coal-fired power plants. Current technologies for the post-combustion CO2 capture from flue gas streams can be broadly classified into the three categories: absorption, adsorption, and membrane processes. Despite challenges, CO2 capture by adsorption using solid sorbents and membranes offers opportunities for energy-efficient capture and storage of CO2. Nanoporous materials have attracted tremendous interest in research and development due to their potential in conventional applications such as catalysis, ion-exchange, and gas separation as well as in advanced applications such as sensors, delivery, and micro-devices. In the first part of this dissertation, we will study the synthesis of membranes using an emerging class of nanoporous materials, metal-organic frameworks (MOFs) for carbon dioxide (CO2) separations. Due to the unique chemistry of MOFs which is very different from that of zeolites, the techniques developed for the synthesis of zeolite membranes cannot be used directly. In order to overcome this challenge, a couple of novel techniques were developed: 1) "thermal seeding" for the secondary growth and 2) "surface modification" for the in situ growth. Membranes of HKUST-1 and ZIF-8, two of the most important MOFs, were prepared on porous α-alumina supports using thermal seeding and the surface modification techniques, respectively. The second part of this dissertation demonstrates a simple and commercially viable application of nanoporous materials (zeolite 5A and amine-functionalized mesoporus silica), storing CO2 as a micro-fire extinguishers in polymers. Materialist is observed that by dispersing these highly CO2-philic nanoporous materials in polymer matrices, the propagation of flame was greatly retarded and extinguished. This flame retarding behavior is attributed to the fact that CO2 released from the sorbents (zeolite 5A and mesoporous silica), blocks the flow of oxygen, therefore causing the fire to be effectively extinguished. Our results suggest that the binding strength of CO2 on sorbents play an important role. If the binding strength of CO2 is too low, CO2 releases too early, thereby ineffective in retarding the flame.

The object of this thesis is to get a deeper understanding of the role of modulator agents in the synthesis of Zr- and Hf-based metal-organic frameworks (MOFs) and their impact on framework properties, such as textural properties, stability, hydrophobicity, and catalytic activity. For this purpose, MOFs are investigated that are built up by the commercially available linker 2,5-thiophenedicarboxylate and the Zr6(µ3-O)4(µ3-OH)412+ cluster. With proper choice of the modulator a new structure, namely DUT-126 (DUT = Dresden University of Technology), could be presented in the course of this work, besides the already known polymorphs of DUT-67, DUT-68 and DUT-69. Furthermore, DUT-67 is chosen as a model structure to functionalise the metal cluster of the framework by exchanging the modulator post-synthetically with hydrophobic fluorinated monocarboxylic acids. With the introduction of these fluorinated molecules, the surface polarities and the stability against water removal can be tuned. In addition, the metal clusters of DUT-67 were modified with a complete removal of the pristine modulator molecules by means of an acidic treatment in order to generate open metal sites that can function as Lewis acid sites. The suitability of DUT-67 and its acid treated analogues as heterogenous catalyst was tested on the Meerwein-Ponndorf-Verley reduction of cyclohexanone. Furthermore, the UiO-67 analogue DUT-122, which contains the luminescent linker 9-fluorenone-2,7-dicarboxylate, was tested as sensor material to detect solvent vapours. It could be shown that DUT-122 is sensitive to various solvent vapours, which induce photoluminescent shifts and intensity changes of the fluorescence emission profile depending on the polarity and the functionality of the respective solvent.