The development of the new cathode and anode materials of Lithium-Ion Batteries (LIBs) with high energy density and outstanding electrochemical performance is of substantial technological importance due to the ever-increasing demand for economic and efficient energy storage system. Because of the abundance of element sulfur and high theoretical energy density, Lithium-Sulfur (Li-S) batteries have become one of the most promising candidates for the next-generation energy storage system. However, the shuttling effect of electrolyte-soluble polysulfides severely impedes the cell performance and commercialization of Li-S batteries, and significant progress have been made to mitigate this shuttle effect in the past two decades. Coordination polymers (CPs) or Metal-organic Frameworks (MOFs) have been attracted much attention by virtue of their controllable porosity, nanometer cavity sizes and high surface areas, which supposed to be an available material in suppressing polysulfide migration. In this thesis, we investigate different mechanisms of mitigating polysulfide diffusion by applying a layer of MOFs (including Y-FTZB, ZIF-7, ZIF-8, and HKUST-1) on a separator. We also fabricate a new free-standing 2D coordination polymer Zn2(Benzimidazolate)2(OH)2 with rich hydroxyl (OH-) groups by using a simple, scalable and low cost method at air/water surface. Our results suggest that the chemical stability, the cluster morphology and the surface function groups of MOFs shows a greater impact on minimizing the shuttling effect in Li-S batteries, other than the internal cavity size in MOFs. Meanwhile, the new design of 2D coordination polymer efficiently mitigate the shuttling effect in Li-S battery resulting in a largely promotion of the battery capacity to 1407 mAh g-1 at 0.1 C and excellent cycling performance (capacity retention of 98% after 200 cycles at 0.25C). Such excellent cell performance is mainly owing to the fancying physical and chemical structure controllability of MOFs or CPs, which has substantial potential for future commercial utilizations.

Manta Flow is a tool for analyzing data flow in enterprise environment. It features Java scanner, a module using static analysis to determine the flows through Java applications. To analyze an application using some framework, the scanner requires a dedicated plugin. Although Java scanner provides plugins for several frameworks, to be usable for real applications, it is essential that the scanner supports as many frameworks as possible, which requires implementation of new plugins. Application using Apache Spark, a framework for cluster computing, are increasingly popular. Therefore we designed and implemented Java scanner plugin that allows the scanner to analyze Spark applications. As Spark focuses on data processing, this presented several challenges that were not encountered in other frameworks. In particular it was necessary to resolve the data schema in various scenarios and track the schema changes throughout any operations invoked on the data. Of the multiple APIs Spark provides for data processing, we focused on Spark SQL module, notably on Dataset, omitting the legacy RDD. We also implemented support for data access, covering JDBC and chosen file formats. The implementation has been thoroughly tested and is proven to work correctly as a part of Manta Flow, which features the plugin in...

The controlled assembly of molecular building blocks is an emerging strategy that allows for the preparation of materials with tailor-made properties. This involves the precise combination of molecular subunits that interact with one another via specifically designed reactive sites. Such a strategy has produced materials exhibiting remarkable properties, including those based on metal-organic frameworks and single-molecule magnets. The present Thesis aims to highlight how such metal-organic assemblies can be engineered at the molecular level to promote certain desired functionalities. Specifically, Chapter 2 will focus on the confinement effects of a crystalline sponge on a ferrocene-based guest molecule that is nanostructured within the porous cavities of a host material. In doing so, we evaluate how one can exert some level of control over the binding sites of the guest molecule, through the addition of electron-withdrawing groups, as well as tuning the physical properties of the guest itself through molecular encapsulation. Notably, we demonstrate a distinct change in the dynamic rotational motion of the ferrocene molecules once confined within the crystalline sponge. In Chapter 3, we investigate the generation of slow relaxation of the magnetization from a Co(II)-based metal-organic framework. We compare this to a closely related 2D Co(II) sheet network, and how slight changes in the crystal field, probed through computational methods, can impact the magnetic behaviour. This type of study may be particularly beneficial in the optimization of single-ion magnets, by sequestering metal centres in select chemical environments, and minimizing molecular vibrations that may offer alternative magnetic relaxation pathways. We extend these principles in Chapter 4, through the use of a nitrogen-rich ligand that acts as a scaffold for Ln(III) ions, thereby yielding 0D and 1D architectures. The coordination chemistry of Ln(III) ions with N-donor ligands remains scarce, especially when evaluated from a magnetic perspective, and therefore, we sought to determine the magnetic behaviour of such compounds. The monomeric unit displays clear single-molecule magnet behaviour with an energetic barrier for the reversal of the magnetization, while the 1D chain displays weaker magnetic characteristics. Nevertheless, such compounds incorporating nitrogen-rich ligands offer much promise in the design of environmentally-friendly energetic materials. In Chapter 5, we take a look at different two different systems that involve the formation of radical species. On one hand, we can promote enhanced magnetic communication between Ln(III) ions, which is typically quite challenging to achieve given the buried nature of the 4f orbitals, and on the other hand, we rely on a redox-active ligand to design stimuli-responsive metal-organic assemblies. The latter case provides access to “smart” molecular materials that can respond to changes in their environment. Here, a multi-stimuli responsive nanobarrel was studied, which displayed sensitivity to ultraviolet radiation, heat and chemical reduction. Lastly, Chapter 6 provides a new method for the systematic generation of cationic frameworks, termed Asymmetric Ligand Exchange (ALE). This strategy focuses on the replacement of linear dicarboxylates with asymmetric linkers that features one less negative charge, in order to tune the ionicity of porous frameworks. This allows for the retention of the structural topology and chemical reactivity of the original framework, representing distinct advantages over other similar strategies. Methods to retain permanent porosity in such cationic frameworks are also proposed. Altogether, these studies highlight how the directed assembly of ordered networks can generate varied properties of high scientific interest.

Die Anzahl von Frameworks zur Erstellung von Web-basierten Anwendungen im Umfeld von Java und J2EE ist inzwischen kaum noch zu überschauen. Regelmäßig kommen neue Frameworks hinzu. Dabei unterscheiden sich diese Frameworks nicht nur auf Ebene von Detaileigenschaften, technischen Qualitäten oder Anwendungsschwerpunkten – es werden auch äußerst unterschiedliche Grundkonzepte verwendet. Ziel dieser Arbeit ist es, aufbauend auf diesen unterschiedlichen Grundkonzepten, eine Klassifikation zu entwickeln, in welche sich jedes beliebige Web-Framework einordnen lässt. Danach werden die wichtigsten Frameworks aus dem Open-Source-Bereich vorgestellt und in die zuvor entwickelte Klassifikation eingeordnet. Im anschließenden praktischen Teil wird eine kleine Web-Anwendung prototypisch mit Hilfe ausgewählter Vertreter verschiedener Klassifikationskategorien implementiert, um diese zu vergleichen und zu bewerten. Ziel ist es, Auswahlrichtlinien für die verschiedenen Kategorien von Web-Frameworks abzuleiten und so die Framework-Auswahl zu unterstützen.

3D JavaScript frameworks are used for creating interactive 3D in web applications. There are two prominent frameworks: Babylon.js and Three.js. They are often compared to one another where performance and ease of use are mentioned as important factors.  A web developer could face choosing a 3D framework. This thesis aims to aid in that process. It investigates how Babylon.js compares to Three.js when it comes to performance such as memory use and frames per second for the end-user consuming a web app. It also investigates how they compare when it comes to ease of use for the developer in terms of initial learnability.  For the performance part, a web app with a minimalistic one box animation was created with each framework and deployed on Netlify. The web app was accessed with a browser’s developer tools to record memory and frames per second. For the ease of use part, observation sessions were made with nine developers who were tasked with getting a basic 3D model up and running locally with each framework with the official documentation as a starting point, one hour limit respectively.  Results showed that both frameworks performed equally when it came to frames per second, and Babylon.js used 2,2 MB, 46 %,  more memory. Only five out of eight or 63 % of the participants managed to implement a 3D model in Babylon.js and five out of nine or 56 %  in Three.js. Three.js scored slightly higher on ease of use than Babylon.js, but neither framework scored high on the overall scale. Participants favoured Babylon.js when asked to choose. However, almost all had a frustrating experience with both during the sessions. Performance is similar except for memory use when it comes to lightweight implementations in these frameworks. Initial learnability could be a gatekeeper. If users do not get past the first hurdle fast with quick feedback that a framework works in the most basic sense, a conceivable risk is they could give up and never use it.

Philosophiae Doctor - PhD / The application of porous materials into industrial hydrogen (H2) storage systems is based on their use in combination with high-pressure cylinders. The processing of metal-organic frameworks (MOF) powders into shaped forms is therefore imperative in order to counteract the adverse effects of poor packing of powders in cylinders. The fabrication of shaped MOFs has, however, been shown to be accompanied by compromised properties such as surface areas, gravimetric and volumetric H2 capacities, and also the working/deliverable H2 capacities in comparison to MOF powders.

Les réseaux métallo-organiques (MOF) sont une nouvelle classe de matériaux poreux hybrides. Néanmoins leurs propriétés uniques introduisent également des difficultés significatives dans la caractérisation par adsorption de gaz. Dans cette thèse, la création d'un code source libre est détaillé, pour standardiser le traitement des isothermes. En utilisant ce code, un traitement à haut débit de plus de 18 000 isothermes est utilisé pour explorer l'échelle d'incertitude présente dans les données publiées sur l'adsorption dans les matériaux poreux. De plus, la mesure directe de l'enthalpie différentielle de l'adsorption en utilisant la microcalorimétrie s'avère être un excellent moyen d'obtenir la contribution des interactions particulières sur l'énergie d'adsorption. Ensemble, ces méthodes peuvent être utilisées pour étudier les sources d'incertitude des MOF. On étudie d’abord l’impact des défauts structurels au moyen d’une méthode post-synthétique alternative de génération de linker/cluster manquants dans l'UiO-66(Zr). Le traitement des matériaux pour leurs utilisations dans un environnement industriel par façonnage est étudié ici sous l’effet de la granulation par voie humide sur trois MOF topiques (UiO-66(Zr), MIL-100(Fe) et MIL-127(Fe)). Enfin, les comportements contre-intuitifs intrinsèques aux cristaux poreux «souples» sont étudiés, où la structure elle-même est responsable de la fluctuation dans les isothermes d'adsorption. Ici, une étude fondamentale sur un matériau flexible DUT-49 (Cu), apporte des informations sur la source de flexibilité induite par adsorption et sa changeabilité par modification structurelle / Metal organic frameworks (MOF) are novel adsorption materials with unique and desirable properties. However, structural defects, processing and structural compliance can lead to irreproducibility in adorption measurements. In this thesis, the creation of an open-source codebase is detailed, which is intended to standardize the processing of isotherms. Using this framework, high throughput processing of over 18 000 isotherms is used to explore the scale of uncertainty present in published adsorption data. Then, direct measurement of the differential enthalpy of adsorption using microcalorimetry is shown to be an excellent avenue of obtaining further insight into the contribution of guest-host and host-host interactions to the overall energetics of adsorption. Together, these methods are used to study some of the sources of the variability of MOFs, and quantify their effect. First, the impact of structural defects is investigated, through an alternative post-synthetic method of missing linker/cluster generation in the prototypical UiO-66(Zr) MOF. The processing of materials for their use in an industrial environment through shaping is another potential source of performance modification, which is here studied as the effect of wet granulation on three topical MOFs (UiO-66(Zr), MIL-100(Fe) and MIL-127(Fe)). Finally, counterintuitive behaviours intrinsic to ``soft'' porous crystals are investigated, where the structure itself is responsible for fluctuation in adsorption isotherms. A fundamental study on a copper paddlewheel based material, DUT-49(Cu) yields know-how on the source of adsorption induced compliance and its tunability through structural modification

Porous solids are a class of materials of high scientific and technological significance. Indeed, they have the ability to interact with atoms, ions or molecules not only at their surface but also throughout the bulk of the solid. This ability places these materials as a major class involved in many applications such as gas storage and separation, catalysis, drug delivery and sensor technology. Metal-Organic Materials (MOMs) or coordination polymers (CPs) are crystalline compounds constructed from metal ions or clusters and organic components that are linked via coordination bonds to form zero-, one-, two or three-periodic structures. Porous Metal-Organic Materials (MOMs) or Metal-Organic Frameworks (MOFs) are a relatively new class of nanoporous materials that typically possess regular micropores stable upon removal of guests. An extraordinary academic and industrial interests was witnessed over the past two decades and is evidenced by a fantastic grow of these new materials. Indeed, due to a self-assembly process and readily available metals and organic linkers, an almost infinite number of materials can, in principle, be synthesized. However, a rational design is very challenging but not impossible. In theory, MOMs could be designed and synthesized with tuned functionalities toward specific properties that will determine their potential applications. The present research involves the design and synthesis of functional porous Metal-Organic Materials that can be used as platforms for specific studies related to many applications such as for example gas storage and particularly hydrogen storage. In this manuscript, I will discuss the studies performed on existing major Metal-Organic Frameworks, namely Zeolite-like Metal-Organic Frameworks (ZMOFs) that were designed and synthesized in my research group. My research was also focused on the design and the synthesis of new highly porous isoreticular materials based on Metal-Organic Polyhedra (MOP) where desirable functionality and unique features can be introduced in the final material prior and/or after the assembly process. The use of hetero-functional ligands for a rational design toward binary or ternary net will also be discussed in this dissertation.

This thesis deals with the analysis of actual situation in the sphere of online betting and implements the web system for the support of activities which are connected to it. The first part of the thesis describes the procedures of obtaining all the needed information and requirements for the target group of users. Subsequently after using this acquired knowledge the new system is designed with the help of the object-orientated programming. At the end the result is the new designed system which is implemented by modern web tools in the leading position with the popular frameworks.

When developers or organizations need to develop a game, simulation or a similar project, they phase the question of whether or not to use a game engine as well as the question on which one to use. Are all game engines the same or does the architecture change and how is the game design different between various game engines? The objective of this thesis is to research these questions as well as giving a concrete understanding of the impact of picking one engine over the other and how each engine influences the way games are developed and answer some more specific questions regarding architecture and usability.  A project was designed with the goal of developing a game. This game was developed by two separate teams over a period of 6 weeks, using two different game engines. The development was split into separate iterations done simultaneously between the teams and questionnaires were filled in to gather data. The game engines used for projects had similarities but also things which were different. Each engine offered ways to speed up development by allowing the developer to reuse and distribute changes among objects to reduce work. The differences caused one engine’s code architecture to be more complex than the other while allowing a better code structure as well as adding more time to learn how the engine handles certain things such as collisions. In conclusion, there is an importance to properly evaluating different game engines depending on the project a developer or organization is creating, not evaluating this properly will impact development speed and project complexity. Even though each engine has their differences, there is no superior game engine as it all depends on the project being developed. The game developed for this project was only touching on certain areas related to 2D games.