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Metal-organic frameworks (MOFs) have attracted much attention in the past few decades due to their ordered, crystalline nature, synthetic tunability, and porosity. MOFs represent a class of hybrid inorganic-organic materials that have been investigated for their applications in areas such as gas sorption and separation, catalysis, drug delivery, and electron or proton conduction. It has been the goal of my graduate research to investigate MOFs for their ability to transport electrons and store and separate gases for ultimate catalytic applications in alternative energy generation. I aim to provide new insight into the design and development of stable MOFs for such applications. We first investigated a cobalt(III) porphyrin based MOF comprised of Co(II)-carboxylate nodes, designated as CoPIZA, for its electron transport capabilities. Thin films of CoPIZA were formed solvothermally on conductive fluorine-doped tin oxide (FTO) substrates and used for electrochemical characterization. Electrochemistry coupled with spectroscopic analysis of the CoPIZA film revealed reversible reduction of the cobalt centers of the porphyrin linkers with maintenance of the overall framework structure. The mechanism of charge transport throughout the film was facilitated by redox hopping of electrons between the metal centers of the nodes and linkers. The ability to incorporate desired properties, such as pore functionalities or open metal centers, into frameworks makes them attractive for applications in separation of gaseous mixtures, such as CO2/N2 from combustion power plants. To investigate the selective adsorption properties, we performed gas sorption measurements on bulk MOF materials to determine their affinity toward CO2. Two Zn-based MOFs containing 2,5-pyridine dicarboxylate linkers were prepared in our laboratory and contained unsaturated Zn(II) metal centers, which possess a binding site on the metal without an activation procedure to remove bound solvent molecules. These MOFs were compared to the well-known Zn-based MOF-69C containing 1,4-benzene dicarboxylate linkers. Thermodynamic analysis of the gas sorption data revealed that the mechanism of CO2 binding involved the coordinatively unsaturated Zn(II) center. The microporous MOF also demonstrated selectivity for CO2 over N2 under the same conditions. As these materials were able to uptake CO2, their ability to transport electrons was also investigated for ultimate applications in catalysis. Electrochemical impedance spectroscopy was performed on the bulk MOF powders and was coupled with solid-state nuclear magnetic resonance spectroscopy. These results determined that the conduction mechanism proceeded via solvent molecules within the pores of the framework. The catalytic ability toward water oxidation of two MOFs was investigated electrochemically. Initial studies focused on a cobalt-based MOF comprised of 2-pyrimidinolate (pymo) linkers, designated as Co(pymo)2, which was prepared on FTO via drop-casting and used for electrochemical experiments. At applied anodic potentials, the CoII centers of Co(pymo)2 became oxidized to form a Co-oxide species on the electrode surface, which was found to be the active catalysis for water oxidation. Further investigations utilized a notably more stable Zr-based MOF with nickel(II) porphyrin linkers, designated as PCN-224-Ni. PCN-224-Ni was prepared solvothermally on FTO and used directly for electrochemical water oxidation. The mechanism of water oxidation at PCN-224-Ni proceeds via oxidation of the porphyrin macrocycle followed by binding of water to the Ni(II) center. Cooperative proton transfer to the Zr-oxo node facilitated water oxidation with the eventual release of O2. Thorough characterization revealed that PCN-224-Ni retained its structural integrity over the course of electrochemical catalysis. These results have allowed us a deeper understanding of the mechanisms of electron transport and conduction throughout frameworks. Specifically, the incorporation of metalloporphyrin molecules with redox active metal centers coupled with the presence of redox active metal nodes resulted in redox hopping charge transport throughout the MOF. In addition, the presence of solvent molecules in the pores of the framework provided an extended network for charge transport. We have gained insight into the structure-function relationship of MOFs for applications in selective gas sorption, where an unsaturated metal center serves as the binding site for gas molecules. Finally, through selection of the components that comprise the framework, a stable metalloporphyrin MOF was found to be capable of electrochemically facilitating the water oxidation reaction. As a result, we have gained valuable insight into the properties of frameworks necessary for charge transport and stability, which will allow for further improvements in the smart design of MOFs for catalytic applications. / Ph. D.

A highly porous metal–organic framework Cu2(BBCDC) (BBCDC = 9,9′-([1,1′-[b with combining low line]iphenyl]-4,4′-diyl)[b with combining low line]is(9H-[c with combining low line]arbazole-3,6-[d with combining low line]i[c with combining low line]arboxylate) (DUT-49) with a specific surface area of 5476 m2 g−1, a pore volume of 2.91 cm3 g−1, a H2 excess uptake of 80 mg g−1 (77 K, 50 bar), a CO2 excess uptake of 2.01 g g−1 (298 K, 50 bar) and an exceptionally high excess methane storage capacity of 308 mg g−1 (298 K, 110 bar) was obtained using an extended tetratopic linker. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Le mémoire est consacré à l'étude numérique des phénomènes survenant à l'interface solide-fluide. Trois processus ont été étudiés: auto-organisation de films moléculaires sur un substrat solide, adsorption du gaz moléculaires dans un matériau nanoporeux et la cristallisation à l'interface organique/inorganique. L'étude de l'auto-organisation et des transitions de phase dans des multicouches de l'azote moléculaires adsorbées sur graphite est présentée dans le chapitre III. L'analyse est focalisée sur l'hétérogénéité spatiale du système et son influence sur le mécanisme et température de transitions ordre/désordre et la fusion des couches. Elle complète ainsi l'étude numérique du diagramme de phase de l'azote moléculaire, bien connu pour le matériau massif (3D) et les monocouches (2D) adsorbées sur un substrat. Le chapitre IV présente une étude de cinétique du mélange des gaz (méthane et méthyle-mercaptan) confiné dans les nanopores de carbone (pores en forme de fentes, de dimensions latérales finies et largeur nanométrique). L'étude porte sur la capacité de stockage de pores, la dynamique des composantes du mélange des gaz sous confinement et l'évaluation de la quantité de l'odorant nécessaire pour une détection facile en cas de fuite. Chapitre V résume les résultats de l'étude préliminaire ayant pour but la mise en place des simulations de biomineralization à l'interface organique/inorganique. Les structures secondaires de deux biomolécules, human leucine-rich peptide hLRAP et full length amelogenin, rM179 ont été prédéterminées. Les plus probables configurations ont été optimisées dans un environnement aqueux. / The present work is devoted to computer simulations of phenomena occurring at solid-fluid interfaces. Three processes have been studied in details: auto organization of molecular films at a solid substrate, adsorption of molecular gas in confined geometry and crystal formation at organic-inorganic interface. Two classical simulation methods have been used: stochastic Monte Carlo and deterministic Molecular Dynamics.The study of self-organisation and phase transitions in molecular nitrogen multilayers adsorbed on the basal plane of graphite is presented in chapter III. It focusses on the systems' spatial heterogeneity and its influence on temperatures of order-disorder and melting transitions. This study completes the numerical analysis of molecular nitrogen phase diagram, well described and understood for 3d (bulk) and 2D (monolayer film) systems.The analysis of kinetics of fluid confined in nanopores is presented in chapter IV. The working case consists of methane-methyl mercaptan mixtures confined in slit-shaped carbon nanopores. Simulations focused on both: storage capacity of carbon pores of finite size and nanometric width, and dynamics of gas mixture components under confinement. An evaluation of odorant content necessary for easy gas leak detection is presented.Chapter V gathers the results of calculations performed to set up the simulations of biomineralization at the organic-inorganic interface. The secondary structures of two amelogenins (human leucine-rich peptide, hLRAP, and full length amelogenin, rM179) have been predicted. The most probable structures have been further refined and the chain folding optimized in aqueous environment.

L'objet de cette thèse est l'étude des possibles mécanismes élastiques expliquant l'amplification du bruit ambiant au droit de certains réservoirs multi-phasiques. Trois jeux de données sont traités. La signature spectrale observée d'un réservoir de vapeur géothermique est différente de celle d'un stockage de gaz. Dans une approche empirique, un algorithme de classification permet d'extraire et de cartographier les anomalies que l'on présume liées au réservoir. Un travail de modélisation est effectué pour tenter d'expliquer les anomalies mesurées. Dans les données réelles, une forte présence de modes supérieurs d'ondes de Rayleigh est détectée. On modélise numériquement en 2D la propagation de ces modes à travers un réservoir placé au sein d'une structure géologique réaliste. La réponse simulée du réservoir se révèle trop faible par rapport aux observations de terrain. Néanmoins, on parvient à inverser les faibles perturbations d'amplitude synthétiques pour la position du réservoir, dans des modèles de référence simples. Cette méthode pourrait être utilisable pour l'imagerie à partir de faibles variations d'amplitudes dans le cadre du monitoring. Pour ce qui est de fortes anomalies observées sur le terrain , il est à noter que les effets visco-élastiques, les effets 3D, et les effets liés à un éventuel champ incident diffus n'ont pas été pris en compte dans la modélisation. Ainsi ce travail n'exclut pas la possibilité de telles anomalies liées à la présence d'un réservoir. / This PhD work investigates the possible elastic mechanisms behind the ambient noise amplification above multi-phase fluid reservoirs. Three datasets are analysed above different reservoirs. The observed spectral signature is different in the gas storage and geothermal contexts. A non-supervised algorithm for amplitude spectrum classification is developed, allowing to extract and map the relevant attributes of a multi-phase fluid presence. As a first modelling step, a wavefield characterisation methodology is applied to determine the composition of the ambient noise. It reveals the presence of strong Rayleigh overtones. Numerical 2D elastic modelling is used to simulate the propagation of overtones across a reservoir within a realistic geological structure. The modelled reservoir response is too small compared to the real data. However, the small amplitude perturbations arising in the numerical simulations are successfully inverted for the position of the reservoir, in simple background models. The developed method could in theory be used for imaging small time-lapse amplitude variations (monitoring), despite the obstacles remaining to be overcome before a real-data application. Neither visco-elastic nor 3D effects are adressed. Thus this work does not exclude the possibility of strong reservoir-specific spectral anomalies.

Depuis près de 55 ans, TIGF exploite, dans le sud-ouest de la France deux stockages de gaz naturel en aquifère. Le gaz stocké est essentiellement composé de méthane (CH4 à plus de 90 %), mais il contient également d’autres hydrocarbures légers (< C4H10), du diazote (N2), du dioxyde de carbone (CO2), de produits soufrés (H2S, mercaptans) et des composés métalliques présents sous formes de traces ou ultra-traces. L’objectif de la thèse est l’étude du transfert de ces composés vers l’aquifère avec comme cas d’étude : le mercure. Un dispositif expérimental a donc été conçu et développé pour (i) mesurer la solubilité dans l’eau du mercure gazeux présent dans le gaz stocké, ainsi que (ii) pour étudier les phénomènes d’adsorption sur la roche dans les conditions de pression (60 bar) et de température (45°C) du réservoir naturel. Les résultats expérimentaux obtenus en laboratoire ont été utilisés dans un modèle numérique afin de simuler le comportement du réservoir et évaluer notamment les quantités de mercure susceptibles de rester en son sein lors de l’exploitation du stockage. / For nearly 55 years, TIGF operates two gas storages in an aquifer in the southwest of France. The stored gas is mainly composed of methane (CH4 over 90%) but it also contains other light hydrocarbons (<C4H10), nitrogen (N2), carbon dioxide (CO2), sulfur compounds (H2S, mercaptans) and some metallic compounds at traces or ultra traces level. The objective of this thesis was to study the transfer of these compounds to the aquifer with special regard to mercury. An experimental device has been designed and developed to measure (i) the mercury solubility in water and (ii) to study the phenomena of adsorption on the rock in the natural reservoir’s conditions (60 bar and 45°C). The laboratory results were used in a numerical code to simulate the behavior of the reservoir and assess the mercury amount that may remain in it during the storage operation.

The research presented in this thesis aims to determine the effectiveness of the uptake of toxic gases by several MOFs for future use in gas-mask cartridges, and to attempt to compensate for any deficiencies they show in “real-world” conditions. The main findings of this thesis confirm that MOFs are suitable candidates for the use in respirator cartridge materials and provide high capacity for adsorption of toxic gases like ammonia and STAM-1 in particular showed an impressive improvement in humid conditions, which normally decrease the performance of MOFs made from the same materials, such as HKUST-1. STAM-1's improved performance in humid conditions is attributed to the structural shift it displays upon dehydration and rehydration and this was shown to be the case in a structural analogue, CuEtOip, which was synthesised in the author's research group. This analogue was analysed using a combination of single crystal XRD and solid state MAS-NMR, both of which showed the structural change occurring and displays similar gas sorption behaviours, suggesting that this mechanism is the source of STAM-1's improved performance in humid conditions. This thesis also examines the “Armoured MOF” process and investigates the transferability of the process of deposition of mesoporous silica onto MOFs with vastly different properties and synthetic methods compared to those published in the original publication. Alongside this, attempts to protect MOFs using mesoporous silicates were investigated for their viability.

The diploma thesis is concerned with the issue of investments decision and capital investment planning. The aim of the thesis is to evaluate a possible investment in the underground gas storage Rožná. The thesis is divided into three parts. The first theoretical part deals with the characterization and terms defining in the field of investments decision. It also mentions the methods how to evaluate the effectiveness of investments decision. The second theoretical part discusses the strategic analysis of gas industry with the emphasis on using of the underground gas storages in the Czech Republic and in other countries within the European Union. The third part analyzes the effectiveness evaluation of the investment while applying the terms of both theoretical parts.

Ziel der durchgeführten Arbeiten war die Etablierung neuer Synthesestrategien zur Gewinnung chiraler metall-organischer Gerüstverbindungen (engl: Metal-Organic Frameworks, MOFs). Hierfür wurden drei verschiedene Ansätze verfolgt. Zunächst sollte die Einbringung einer chiralen Dicarbonsäure mit einem 2,2´-Spirobiindan-Gerüst in ein MOF-Netzwerk untersucht werden. Im Rahmen einer Kooperation wurden neue mit chiralen Oxazolidinonen substituierte 4,4´,4´´-Benzol-1,3,5-triyl-tribenzoesäuren H3ChirBTB-n (n = 1, 2) entwickelt, die ebenfalls zur Synthese neuer chiraler MOFs dienten. Die Modifizierung bekannter nicht-chiraler metall-organischer Gerüstverbindungen mit koordinativ ungesättigten Metallatomen durch Anbindung chiraler Amine stellte die dritte Synthesestrategie dar. Im Rahmen der letztgenannten Syntheseroute wurde für MIL-101 (MIL = Matérial Institut Lavoisier) eine sehr hohe katalytische Aktivität in der Cyanosilylierung von Benzaldehyd nachgewiesen. Die Umsetzung mit chiralen Aminen führte jedoch nicht zu einem enantioselektiven Katalysator. Im Gegensatz dazu konnten die ersten beiden Synthesewege zur Gewinnung neuer chiraler metall-organischer Gerüstverbindungen erfolgreich beschritten werden. Durch solvothermale Reaktion von (S)-2,2´-Spirobiindan-5,5´-dicarbonsäure ((S)-H2Spiro-BIDC) mit Zinknitrat in N,N-Dimethylformamid (DMF) wurde eine neue chirale metall-organische Gerüstverbindung namens DUT-7 (DUT = Dresden University of Technology) der Zusammensetzung Zn4O((S)-Spiro-BIDC)3 dargestellt. Neben einer unerwarteten, zweifach interpenetrierten Netzwerkstruktur mit hexagonalen Kanälen weist DUT-7 eine für MOFs bislang noch nicht beobachtete temperaturinduzierte, reversible Strukturänderung auf. Die zweite neue Strategie zur Gewinnung chiraler MOFs beinhaltete die Umsetzung der chiralen Tricarbonsäuren H3ChirBTB-n, die entweder (S)-4-iso-Propyl- (n = 1) oder (S)-4-Benzyl-1,3-Oxazolidin-2-on-Substituenten (n = 2) tragen. Die beiden gewonnenen Verbindungen Zn3(ChirBTB-1)2 und Zn3(ChirBTB-2)2 weisen trotz gleicher Zusammensetzung völlig unterschiedliche Kristallstrukturen auf. Beide Materialien wurden erfolgreich in der Mukaiyama-Aldol-Reaktion von Benz- bzw. 1-Naphthaldehyd mit 1-Methoxy-2-methyl-1-(trimethylsiloxy)propen eingesetzt, wobei ihre katalytische Aktivität mit verschiedenen Referenzkatalysatoren verglichen wurde. Die erzielten Enantiomerenüberschüsse (ee) liegen zwischen 6 und 16%. Auf der Suche nach neuen, für die Einbringung der ChirBTB-n-Liganden geeigneten MOF-Strukturen wurde auch die Umsetzung der reinen, nicht chiralen 4,4´,4´´-Benzol-1,3,5-triyl-tribenzoesäure (H3BTB) untersucht. Die Reaktion mit Nickelnitrat führte zur Bildung einer neuen hochporösen Verbindung namens DUT-9 mit der Zusammensetzung Ni5O2(BTB)2(DEF,DMF)4(H2O)4. DUT-9 weist neben den auf dem Gebiet der MOF-Forschung bislang unbekannten Ni5O2-Clustern eine noch nicht beschriebene dreidimensionale (3,6)-Netzwerktopologie auf. Das neue Material zeigt zudem exzellente Speicherkapazitäten für Wasserstoff, Methan und Kohlenstoffdioxid. / The present work aims on the search for new synthesis strategies towards chiral Metal-Organic Frameworks (MOFs). Three different approaches were pursued. Initially, the integration of a chiral dicarboxylic acid with a 2,2´-spirobiindane backbone into a MOF network was investigated. Within a cooperation, new 4,4´,4´´-benzene-1,3,5-triyl-tribenzoic acids H3ChirBTB-n (n = 1,2) with chiral oxazolidinone substituents were developed which were also used for the assembly of chiral MOFs. The third synthesis strategy involved the tethering of chiral amines to coordinatively unsaturated metal atoms of known non-chiral Metal-Organic Frameworks. Within the last-mentioned approach, the very high catalytic activity of MIL-101 (MIL = Matérial Institut Lavoisier) towards the cyanosilylation of benzaldehyde was demonstrated. Treatment with chiral amines did not lead to an enantioselective catalyst. In contrast, the first two synthesis strategies could be performed successfully. A new MOF named DUT-7 (DUT = Dresden University of Technology) with composition Zn4O((S)-Spiro-BIDC)3 was obtained by solvothermal reaction of (S)-2,2´-spirobiindane-5,5´-dicarboxylic acid ((S)-H2Spiro-BIDC) with zinc nitrate in N,N-dimethylformamide (DMF). Besides an unexpected, two-fold interpenetrated framework structure with hexagonal channels, DUT-7 shows a temperature induced, reversible structure transformation not yet observed. The other new strategy to obtain chiral Metal-Organic Frameworks involved the conversion of the chiral tricarboxylic acids H3ChirBTB-n bearing either a (S)-4-iso-propyl- (n = 1) or a (S)-4-benzyl-1,3-oxazolidin-2-one substituent (n = 2). Though having the same framework composition, the new compounds Zn3(ChirBTB-1)2 and Zn3(ChirBTB-2)2 exhibit completely different crystal structures. Both materials were tested in the Mukaiyama aldol reaction between benzaldehyde or 1-naphthaldehyde, respectively, and 1-methoxy-2-methyl-1-(trimethylsiloxy)propene and their catalytic activity was compared to different reference catalysts. Enantiomeric excess values (ee) between 6 and 16% were obtained. In search of new MOF structures being suitable for the integration of the ChirBTB-n linkers, the conversion of the pure, non chiral 4,4´,4´´-benzene-1,3,5-triyltribenzoic acid (H3BTB) was investigated. The reaction with nickel nitrate lead to the formation of a new, highly porous compound Ni5O2(BTB)2(DEF,DMF)4(H2O)4 named DUT-9. Besides Ni5O2 clusters which are a novelty in MOF chemistry, DUT-9 exhibits a three dimensional (3,6)-network topology not yet described. In addition, the new material shows excellent storage capacities for hydrogen, methane and carbon dioxide.

Étant donné que le stockage de gaz naturel ou d’air comprimé dans des niveaux souterrains constitués de sel joue un rôle essentiel pour assurer l'approvisionnement en énergie sur le long terme, le gouvernement chinois a construit de nombreux lieu de stockage dans ces niveaux géologiques ces dernières années. En raison des variations saisonnières de la pression gaz / air, les entrepôts subissent des chargements cycliques qui provoquent la fatigue des roches et conduisent à des risques de rupture qu’il faut maîtriser pour des raisons liées à la sécurité et à l'environnement. La compréhension des processus de fatigue discontinue du sel sous chargement cyclique est donc très importante et fait l'objet de cette étude, qui se concentre sur des recherches expérimentales et le développement de modèles constitutifs décrivant la déformation sous fatigue. Cette thèse s’articule suivant la méthodologie suivante : ① des essais de chargement cyclique classique pour étudier les propriétés basiques de la fatigue dans le sel. ② des tests de charge cyclique discontinu pour explorer les processus de fatigue discontinue. ③ l’instrumentation pour détecter les émissions acoustiques afin de suivre l'évolution des dommages causés par la fatigue dans le sel. ④ Le développement à la base des résultats expérimentaux obtenus de modèle constitutif pour la fatigue discontinue. / Since the salt cavern storage of natural gas and compressed air plays a critical role in ensuring the energy supply and adjusting the seasonal imbalance of power, China government has been constructing numerous new storages in recent years. Because of the seasonal of the seasonal variations of the gas/air pressure, the storages undergo cyclic loading, which causes rock fatigue and induces the associated safety and environmental hazards. The investigation of the discontinuous fatigue of salt under cyclic loading is therefore very important and is the subject of this study, which focuses on the experimental investigations and the development of the constitutive models describing the fatigue deformation. This thesis includes the following principal parts: ① Conventional cyclic loading testing to investigate the basic properties of fatigue in salt. ② Discontinuous cyclic loading tests testing to investigate the discontinuous fatigue. ③ Acoustic emission detecting experimentation to track the evolution of the fatigue damage in the salt. ④ Development of the fatigue life model and constitutive model for the discontinuous fatigue, based on the obtained experimental results.