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With demand for gasoline and diesel expected to decline in the near future, crude-tochemicals technologies have the potential to become the most important processes in the petrochemical industry. This trend has triggered intense research to maximize the production of light olefins and aromatics at the expense of fuels, which calls for disruptive processes able to transform crude to chemicals in an efficient and environmentally friendly way. Simultaneously, the production of high-demand chemical commodities such as olefins, aromatics and gasoline from alternative feedstocks such as methanol has been central to research in both academia and industry. In both conversions, catalyst composition and formulation play a key role. In principle, shaping and optimal compositional formulation are major challenges in the successful industrial application of heterogeneous catalysts. Herein, we evaluate the application of the spray-drying shaping technique to manufacture spherical zeolite-based catalysts and their applicability in the direct crude-to-chemicals and the methanol-to-hydrocarbons processes. A thorough study of the effect of formulated fluid catalytic cracking catalyst composition on the one-step cracking of Arabian light crude oil was studied in the present thesis. Our results demonstrate that over a 35wt.% yield to light olefins can be achieved on spray-dried catalysts containing 1:1 mixtures of ZSM-5 and FAU zeolites. On the other hand, the nature of the selected clay, one of the key components in formulated catalysts, has a significant influence in modifying the final acidity of the composite, which, when applied in methanol to hydrocarbons, results in the propagation of either the alkene or arene cycles. The present PhD thesis also has been dedicated to the study of optimal conditions for the highly selective and stable production of aromatics during methanol to aromatics at high pressure. High selectivity to aromatics (~50%) can be achieved on a commercial high silica ZSM-5 at 400° and 30 bar total pressure. The high partial pressure of primary olefins and the promoted methanol-induced hydrogen transfer pathway result in an exponential increase in aromatization, while the high partial pressure of steam generated via dehydration of methanol leads to in situ coke removal and, therefore, to a slower deactivation of the zeolite.

The rapid global climate change associated with increasing planetary CO$_2$ levels is possibly one of the greatest challenges existing currently. In order to address this grave problem, a variety of solutions and approaches have been proposed. It is likely that a combination of these approaches would be required to solve the multi-dimensional problem of climate change. One potential approach to mitigate carbon emissions is the concept of a ‘Circular Carbon Economy’. This approach encompasses the concept of capturing carbon emissions and reusing the captured CO$_2$ to make fuels and chemicals using renewable energy. Use of fuels and chemicals manufactured via this approach would thus avoid ‘new’ CO$_2$ emissions and prevent the accumulation of additional CO$_2$ in the atmosphere as these products will be CO$_2$-neutral. The use of CO$_2$-neutral fuels would especially be beneficial as not only would it cause a significant impact on CO$_2$ emissions in terms of volume but also it would provide a way to store energy from intermittent sources like solar, wind etc. Furthermore, these fuels can be used without requiring a significant overhaul of the energy infrastructure. One of the most promising routes for the synthesis of fuels and chemicals from CO$_2$ is via the thermal hydrogenation of CO$_2$ using multifunctional heterogeneous catalysis. Multifunctional catalysis refers to the combination of catalysts having different functionalities into a single reactor (one-pot). This catalytic route is a powerful tool for tuning the product distribution during a reaction and for enhancing the yield of target products. Thus, this PhD Thesis describes the design of several multifunctional catalyst combinations which have been applied for producing various hydrocarbon products of interest from CO$_2$ ranging from light olefins, aromatics and fuel range paraffins. The catalyst combinations consisted of a metal/metal oxide and a zeolite and depending on the configuration used, enhanced the selectivity to target products. Various advanced characterization techniques have also been utilized in order to reveal the status of active species and the underlying reaction mechanism(s).

Flavonoids are a specialized group of compounds produced by plants that give them greater adaptability to their environment and ultimately enhance their ability to survive. In plants, one function of flavonoids is to attract pollinators by their various flavor and scent profiles. They also protect the photosynthetic machinery from photo-oxidation. In humans, flavonoids have been shown to act as antioxidants, exhibit antimicrobial activity, and have shown potential as cancer treatments. In nature, flavonoids are most often found coupled with a sugar group (glucose, rhamnose, and others) which imparts stability and increases bioactivity. The process of adding a sugar (glycosylation) is catalyzed by a class of enzymes called glycosyltransferases (GT). One such enzyme found in grapefruit only glucosylates the flavonol class of flavonoids at the 3-OH position and is of interest due to its unique substrate and regio-specificity. Called Cp3GT (Citrus paradisi flavonol 3-O glucosyltransferase), this enzyme is similar in structure to other plant GT’s yet differs in the flavonoids it can glucosylate and where the glucose can be added. To date, the literature has not reported a structural mechanism for a flavonol specific 3-O glucosyltransferase’s unique catalytic activity. High-resolution structural imagery of enzymes, elucidated using X-ray crystallography, can be used to direct custom enzyme development to produce bioavailable natural products. Furthermore, structural research on enzymes with high specificity strengthens enzyme-ligand docking simulations, which are commonly used to test the binding affinity of potential pharmaceuticals. This research hypothesizes Cp3GT has structural features that confer its unique substrate and regiospecificity that are not revealed by homology modeling. This hypothesis will be tested using x-ray crystallography of purified Cp3GT protein bound to its preferred flavonol substrates. The gene for Cp3GT was transformed into Pichia pastoris and was recombinantly expressed using methanol induction. Cp3GT was purified to 80% purity using cobalt metal affinity chromatography. Cp3GT was subjected to additional purification measures using anion exchange chromatography with the goal of increasing purity to ≥95% for crystallization experiments. Purity analysis was conducted using SDS-PAGE (Coomassie/silver stain, western blot) and UV-Vis spectrophotometry. While initial results are promising, additional purification steps may be needed to achieve the purity necessary for crystallization.

Fossil resources provide the raw materials for manufacturing a majority of commodity chemicals and fuels, but the release of this buried carbon accelerates environmental crises related to rising levels of atmospheric CO2. Engineering direct and energy-efficient pathways to synthesize chemicals and fuels from sustainable reagents and using CO2-free renewable energy could mitigate these challenges. Promising strategies for developing such reaction processes utilize non-precious metal catalysts to address kinetic challenges and non-thermal plasma activation to circumvent thermodynamic constraints. Non-precious bimetallic catalysts were employed to selectively convert CO2 with H2 to the building block chemical CO, and in situ X-ray and infrared techniques revealed the properties of the catalytic components. Significant oxygen exchange between the ceria catalyst support material and gas-phase CO2 was quantified under reaction conditions, and NiFe bimetallic catalysts tuned the reaction selectivity while maintaining high activity. In order to eliminate H2 as a reagent, ethane (an underutilized shale gas fraction) was reacted with CO2 to produce alcohols. This reaction is not thermodynamically feasible under mild conditions, so non-thermal/non-equilibrium plasma activation was implemented in order to achieve a one-step, H2-independent process to synthesize alcohols and other oxygenates under ambient temperature and pressure. The ability to use non-thermal plasma to activate N2 at mild conditions introduces the possibility of moving beyond the carbon-based paradigm for chemicals and fuels. Non-thermal plasma has been used to synthesize ammonia under mild conditions, but the dearth of fundamental understanding of plasma-catalyst interactions handicaps the development of plasma catalytic N2 conversion processes. Therefore, an in situ FTIR reactor was employed to identify the surface reaction intermediates during plasma catalytic ammonia synthesis. These results provide the first direct evidence of catalytic surface reactions under plasma activation and reveal the presence of reaction pathways that are distinct from analogous thermocatalytic reactions. Finally, an energy-based analysis evaluates the environmental and economic outlook for plasma-activated nitrogen fixation processes.

La thèse est divisée en deux parties distinctes.La première consiste, après une étude exhaustive concernant les réactions de désulfurisation de thiocétals répertoriées dans la littérature, a montré que l'association TMSCl/NaI est une méthode de choix moderne pour réduire les thiocétals puisqu'elle ne nécessite aucun métal toxique. Dans une plus longue partie, nous nous sommes interressés à la synthèse d'hétérocycles (isocoumarines, benzothiophènes et indoles) par l'étude de réactions originales d'hétérocyclisation. La thèse est présentée sous forme du publications (7). / This thesis is divided into two distinct parts. The first show that, after a comprehensive study of thioketals desulfurization reactions listed in the literature, the use of TMSCl / NaI combination is a modern method of choice to reduce thioketals since it does not require any toxic metal. In a second part, we have been interested in the synthesis of heterocycles (isocoumarins, benzothiophenes and indoles) by the study of original heterocyclization reactions. The thesis is presented with the presentation and discussion of publications (7).

Depuis plusieurs décennies, la catalyse par les métaux de transition est devenue un outil incontournable pour la synthèse organique. Chaque année, des milliers de publications décrivent le développement de nouvelles réactions effectuées en présence de complexes organométalliques. Le premier chapitre de ce manuscrit présente une comparaison générale de la réactivité des métaux du groupe 11 (Cu, Ag, Au), avec une attention particulière sur leur capacité à réaliser des réactions d’activation électrophile (Au) ou des transferts de nucléophiles (Cu). Des exemples représentatifs sont donnés pour illustrer ces concepts. Dans la seconde partie, la synthèse d’allènes et d’énones trifluorométhylés par catalyse à l’or(I) est détaillée. Une méthode générale de préparation d’allènes-CF3 a été développée par un transfert d’hydrure-1,5 induit par un complexe d’or(I). Les limites de la méthode ainsi que certaines applications des produits sont décrites. Dans la même idée, un réarrangement-[3,3] d’acétates propargylique catalysé par l’or(I) a été appliqué à la synthèse d’énones-CF3. L’incorporation de cette méthode dans un processus monotope avec une réaction de Diels-Alder est également présentée. La troisième partie est centrée sur les réactions de borofonctionnalisation d’allènes catalysées par le cuivre(I). Les récents développements de ce domaine sont passés en revue, et notre contribution à ce sujet est détaillée. Enfin, un travail préliminaire sur l’élaboration d’un processus monotope impliquant une catalyse coopérative cuivre(I)/or(I) est présenté. / During the last decades, transition metal catalysis has become an essential tool in organic synthesis. Each year, thousands of publications report the development of new reactions mediated by metal complexes. This manuscript depicts our contribution to this field. The first chapter presents a general comparison of the reactivity of coinage metals (Cu, Ag, Au) complexes in catalysis, with a special focus on their ability to perform electrophilic activation (Au) or nucleophilic transfer (Cu) reactions. Representative examples are given to illustrate these concepts. In the second part of the manuscript, the synthesis of trifluoromethylated allenes and enones by gold(I) catalysis is reported. A general method for the preparation of CF3-allenes has been developed based on a gold(I)-mediated 1,5-hydride shift. The scope and limitations of the method, as well as some subsequent transformations of the products are described. Using similar substrates, a gold(I)-catalyzed [3,3]-acetate rearrangement was applied to the preparation of CF3-enones. The employment of this method into a one-pot procedure involving a subsequent Diels-Alder reaction is also reported. The third part focuses on the copper(I)-catalyzed borofunctionalization of allenes. The recent reports from the literature are reviewed, and our contributions to this area of research are described through the study of a new copper(I)-catalyzed allene boroacylation method. Finally, preliminary results on the elaboration of a copper(I)/gold(I) catalytic one-pot process are presented.

Zeolite-supported transition metal catalysts, which couple the unique size- and shape-selectivity arising from the well-defined microporous structure of zeolites with the inherent high activity of metal species, have demonstrated remarkable performance in numerous catalytic reactions. Conventionally, such catalysts are prepared by loading metal species in the micropores of zeolites in the form of clusters (each containing only several atoms). Despite their high catalytic activity, the ultra-small clusters are usually highly mobile, and tend to migrate from the micropores to the crystal surfaces of zeolite during the reaction, where they agglomerate and deactivate. In this dissertation, we attempted to solve this issue by encapsulating metal nanoparticles (NPs) in zeolite crystals, based on the following considerations: (i) compared to clusters, nanoparticles have similar catalytic activity but much less mobility; and (ii) as long as the active sites are inside the zeolite crystals (not necessarily in the micropores that are too small to accommodate nanoparticles), they can exhibit selectivity associated with the zeolite structure. In the first chapter, we gave a general introduction to zeolites and zeolite supported catalysts, focusing on the preparation of hierarchical zeolites that are the main catalyst support materials used in the research projects of this dissertation. In the second chapter, we encapsulated highly dispersed Pd NPs (~2.6 nm) in zeolite ZSM-5 crystals, and used the obtained catalyst (Pd@SG-ZSM-5) for the hydrogenation of cinnamaldehyde. The confinement effect gave rise to an interesting catalytic behavior: compared with the traditional supported Pd catalyst prepared by impregnation, Pd@SG-ZSM-5 showed a 2.5-fold enhancement in the selectivity of hydrocinnamaldehyde (73% vs. 30%). Liquid adsorption combined with infrared spectroscopy characterization revealed that Pd@SG-ZSM-5 catalyst adsorbs much less reactant and product molecules than traditional catalyst, thereby suppressing the formation of by-products and leading to high selectivity. In chapter three, we developed a new method to encapsulate in situ produced molybdenum carbide (MoCx) in zeolite ZSM-5 for the methane dehydroaromatization (MDA) reaction. In this method, the structure-directing agent used to synthesize hierarchical zeolite ZSM-5 was utilized to reduce molybdenum precursor through a calcination process in an inert atmosphere. The zeolite subsequently underwent a secondary growth process to achieve encapsulation. The catalytic behavior of the as prepared catalyst in MDA consolidate our previous conclusion that MoCx particles outside the microporous channels can also act as the active sites for MDA, whereas it is traditionally viewed that only MoCx clusters inside the micropores are active sites. In addition, the encapsulation strategy allowed us to design experiments to answer one open question related to MDA, namely whether the Brønsted acid (BA) sites of the zeolite play a catalytic role in the conversion of methane to aromatics or only promote the dispersion of the Mo species. We encapsulated MoCx particles, which had proven to be active sites, in pure siliceous zeolite (Silicalite-1) that does not contain BA sites. The catalyst did not exhibit MDA activity even when aromatic compounds were introduced into the system by pre-adsorption or co-feeding, indicating that the BA sites are responsible for the oligomerization/cyclization step during MDA. Finally, in chapter five, we summarized the dissertation and gave our perspectives and outlooks on the further development of encapsulated catalysts based on zeolites.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19515号 / 理博第4175号 / 新制||理||1599(附属図書館) / 32551 / 京都大学大学院理学研究科化学専攻 / (主査)教授 丸岡 啓二, 教授 大須賀 篤弘, 教授 依光 英樹 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM