The never-ending quest to design and produce bespoke materials optimized for specific purposes has recently led to the discovery of a rapidly expanding subclass of porous materials known as Metal-Organic Frameworks (MOFs). The potential of MOFs appears to be immense due to the accessibility of a nearly-infinite number of both organic and inorganic components – building blocks that can be easily self-assembled in extended networks. Taking advantage of modular composition, high surface areas, adjustable pore sizes, and tunable surface properties, MOFs are emerging as one of the most promising materials for energy and environmental applications. \nThe main objective of this thesis is to explore different aspects concerning MOF materials, building on the knowledge from several subtypes of MOFs developed primarily in Prof. Eddaoudi’s group. In particular, this dissertation expands the diversity within and utility of the following MOF subtypes: MOFs comprised of sql supermolecular building layers (SBL), MOFs based on fluorometalates, and zeolite-like MOFs (ZMOFs). \nWhenever feasible, emphasis was placed on the synthesis and application of MOFs as supported thin films, particularly as the sensitive element of capacitive gas sensors or as a selective layer of composite membranes for gas separation. \nSome of the highlights from the results obtained in the course of this study include: \n \n- Introduction of MOFs to the field of reverse selective (CO2/H2) membranes for hydrogen purification. Notably, despite the challenges associated with the preparation of continuous “defect-free” MOF membranes, three different types of adsorption-driven MOF membranes have been synthesized and have shown a preferential permeation of CO2 over H2. In addition, the diffusion driven butane isomers separation was realized in ana-ZMOF membrane, being close to or even overperforming benchmark materials reported in the literature for the separation of both gas pairs. \n- Identification of an appropriate MOF compatible with the developed capacitive-based sensor system and capable of the detection of sulfur dioxide in ppb level. \n- Discovery of a ZMOF material with a new unprecedented zeolitic topology and its ability to separate propylene from propane upon the difference in diffusion of the adsorbates.

Dans cette thèse, de nouvelles stratégies pour la préparation de matériaux de type Metal-Organic-Frameworks (MOF) ont été étudiés et développés. L’électrodeposition bipolaire indirecte (IBED) a été utilisé pour préparer ZIF-8 et HKUST-1 sur des substrats métalliques de façon simple et avec une sélectivité spatiale. Ce concept devrait pouvoir être généralisée pour la synthèse de nombreux autres composés MOF, permettant ainsi une synthèse pas chère et verte, conduisant à de nouvelles générations de composites de type Janus basés sur des MOFs. En outre, des électrodes avec une structure hiérarchique macro-/ microporeux de HKUST-1 ont été préparées par une technique de dissolution-dépôt électrochimique. L'approche de synthèse mis au point est très pratique en ce qui concerne la durée des expériences, et ouvre diverses applications pour les MOFs. Enfin des nanoparticules de métaux nobles sur un substrat à base de MIL-101 ont été préparées comme la dernière partie de l'étude expérimentale par dépôt colloïdal. Ce concept peut être généralisé pour la synthèse d'autres composites nanoparticules métalliques / MOF, et pourrait améliorer l'activité catalytique des MOFs. En dehors de l'étude expérimentale, afin de comprendre mieux la catalyse de matériaux MOF, le comportement catalytique de Cu (II) dans le MOF-505 a été théoriquement étudié pour la réaction d'aldolisation Mukayiama par la théorie de densité fonctionnelle et comparé à celui d'un autre catalyseur, Cu-ZSM-5. En outre, le comportement catalytique d'amas homo- et hétéro-bimétalliques, qui sont des complexes métalliques qui représentent les agrégats métalliques dans les MOFs, a également été étudié théoriquement pour la réaction de cycloaddition de dioxyde de carbone et des oxydes d'éthylène. / In this thesis, new strategies for the preparation of Metal 0rganic Frameworks (MOF) materials with designed structures were studied and developed. Indirect bipolar electrodeposition (IBED) was used to prepare ZIF-8 and HKUST-1 on metal substrates in a straightforward and site-selective way. This concept is expected to be able to be generalized for the synthesis of many other MOF compounds, thus allowing a cheap and green synthesis, leading to new generations of MOF-based Janus-type composites. Furthermore, rationally designed hierarchical macro-/microporous HKUST-1 electrodes were prepared via an electrochemical dissolution-deposition technique. The developed synthesis approach is very practical in terms of the time consumption, and opens up MOFs for various applications. Finally, MIL-101-supported noble metal nanoparticles were prepared as the last part of the experimental studies via a simple colloidal deposition technique. This concept might be generalized for the synthesis of other metal nanoparticle/MOF composites, and might improve the catalytic activity of MOFs. Apart from the experimental study, in order to gain a deeper insight into the catalysis of MOF materials, the catalytic behavior of Cu(II) in the paddle-wheel unit of MOF-505 was theoretically investigated for the Mukaiyama aldol reaction via the density functional theory and compared to that of another catalyst, Cu-ZSM-5 zeolite. Besides, the catalytic behavior of homo-metallic clusters and hetero-bimetallic clusters, that are the metal complexes representing the metal clusters in MOFs, were also theoretically investigated for the cycloaddition reaction of carbon dioxide and ethylene oxides.