No description available.

Phosphotungstic acid H3[PMo12O40](PTA) with the Keggin structure has become well known as a solid superacid with pKa≈-13. Such a strong acidity is caused by delocalization of the negative charge of the anion on many oxygen atoms over the surface of the Keggin structure. High acidity of PTA and its good solubility in water and other polar solvents enables its use as a highly active homogeneous catalyst. However, in spite of relatively higher reaction rate, homogeneous catalysis has various drawbacks that limit its practical application. The main drawback is the difficult and expensive removal of the used catalyst from the reaction mixture and its recycling. PTA also demonstrated good catalytic activity as a heterogeneous catalyst of various organic reactions, e.g. hydrolysis, hydration and polymerization. Wide application of a pure superacid in catalysis is limited by its low surface area and solubility in polar solvents. The objective of this work is the synthesis and study of insoluble superacidic catalysts covalently embedded into the silica matrix. The catalyst PTA/SiO2 was synthesized by the sol-gel method. Tetraethoxysilane was co-condensed with PTA in acidic media in the presence of Pluronic P123 surfactant as a pore-forming agent. The obtained gel was air-dried and calcined at 500 °C producing a mesoporous material with a significant fraction of micropores in its structure. Isotherms of adsorption/desorption of nitrogen indicated cylindrical shape of the pores with necks that is typical for materials obtained with Pluronic P123 as a template. Cs-exchanged material was prepared by mixing PTA/SiO2 with a solution of CsCl. The cation exchange on cesium decreased the total pore volume due to a much higher volume of cesium ions as compared to protons. In addition, partial pore blocking by these ions restricted access to small pores thus reducing accessible surface area. Heteropolyacids are unstable in alkaline media that makes direct solid-state titration impossible. Surface acidity of the samples was determined by reversed titration. Dry samples were dispersed in a solution of pyridine in tetrahydrofuran. After equilibration, the solid phase was filtered, and the filtrate was titrated by HCl. PTA/SiO2 has a very high adsorption capacity on pyridine, which corresponds to 15 molecules of pyridine per [PMo12O40]3- anion. This number exceeded the number of available protons. The catalysts were successfully tested in the alkylation of mesitylene by alkenes. The use of superacidic materials in catalytic reactions can significantly improve the effectiveness of the processes.

<p> The Hammett acidity function, Ho, has been extended from dilute solutions of water in sulfuric acid to the highly acidic HSO3F-SbF5•3SO3 system, a range of more than eight Ho units. The protonation behaviour of eleven aromatic nitro indicators was studied by means of a spectrophotometric technique. These indicators were found to behave in a similar fashion to the previously studied aniline indicators which have been used to define the Ho function from infinitely dilute solutions of acids in water to concentrated sulfuric acid solutions. The superacid systems studied were H2O-H2SO4-SO3, H2SO4-HSO3Cl, H2SO4-HSO3F, H2SO4-HB(HSO4)4, KSO3F-HSO3F, HSO3F-SO3, HSO3F-AsF5, HSO3F-SbF5, and HSO3F-SbF5•3SO3 of which the latter is the most acidic solvent system known.</p> / Thesis / Doctor of Philosophy (PhD)

This study investigated the cracking chemistry as model lipids were reacted over a benchmark catalyst, H-ZSM-5, and two industrially used catalysts, faujasite and silica-alumina. Initial work began with a homogeneous system in which oleic acid, an unsaturated free fatty acid, and triflic acid, a Bronsted superacid, were reacted at low temperatures. Results indicated that protonation began at the double bond with cracking occurring in the direction away from the carboxylic end and producing a multiplicity of branched saturated fatty acids. Heterogeneous cracking on H-ZSM-5 at 400°C indicated that acylglycerides initially crack due to protonation occurring on the outside surface of the catalyst. Secondary cracking formed olefins (C2 – C4) which then oligomerize to form aromatic hydrocarbons that were within the range of components for gasoline. Catalysis using faujasite and silica-alumina indicated that acylglycerides require milder cracking conditions than typical crude petroleum, indicating that lower temperatures and lower catalyst to feed ratios will be required to achieve the same reactant conversions as seen in petroleum refineries.

abstract: This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached. / Dissertation/Thesis / Ph.D. Chemistry 2013

La grande majorité des sucres existe sous forme de glycanes. Ces polysaccharides ou glycoconjugués se composent d'unités monosaccharidiques assemblées par des liaisons covalentes qui sont formées à l'issue de la réaction de glycosylation. Bien qu'abondamment utilisée en synthèse organique, certains détails du mécanisme de cette réaction, qui trouve de nombreuses applications dans le domaine de la santé et des matériaux, restent encore à élucider.En particulier, la mise en évidence d'intermédiaires réactionnels de la glycosylation tels que le cation glycosyle ou ion glycosyl oxocarbénium, une espèce chimique théorique généralement invoquée dans le mécanisme, constitue un enjeu essentiel pour élucider ce mécanisme de cette réaction à l'échelle atomique permettant d'améliorer par la suite l'efficacité de cette réaction pour la synthèse d'oligosaccharides et/ou de glycoconjugués. Plusieurs équipes dans le monde ont tenté de mettre en évidence et d'étudier ces intermédiaires ioniques en utilisant différentes approches mais la durée de vie estimée de ces espèces de l'ordre de la picoseconde a, à ce jour, rendu leur observation expérimentale impossible.Ce travail de thèse a consisté à développer une nouvelle approche qui repose sur la combinaison de deux chimies, la glycochimie et la chimie superacide, et l'utilisation de deux techniques d'analyse, la Résonance Magnétique Nucléaire (RMN) in situ à basse température et les calculs théoriques afin de générer, identifier et caractériser les cations glycosyles. Après avoir synthétisé une série de donneurs de glycosyle protégés, ces derniers ont été traités en milieu superacide de type HF/SbF5. A partir du B-D-glucose et de la B-D-glucosamine, les ions dioxalénium et oxazolinium correspondants ont été obtenus, caractérisés et leur conformation élucidée. Afin d'accéder au cation glycosyle tant recherché, les dérivés 2-déoxy et 2-bromo du D-glucopyranose ont été préparés et soumis aux conditions superacides pour fournir pour la première fois l'ion oxocarbénium. La qualité des spectres RMN obtenus pour chaque espèce combinée aux calculs théoriques ont permis d'identifier et d'étudier en détail les conformations privilégiées de ces ions. Enfin le piégeage de ces ions par des nucléophiles faibles a également permis de confirmer l'impact de la structure de l'ion oxocarbénium sur l'orientation de la liaison anomérique générée. / A vast majority of biologically and therapeutically active carbohydrates exist as glycans (polysaccharides or complex glycoconjugates) in which monosaccharide units are joined via the glycosylation reaction. But surprisingly the details of the glycosidic bond formation remain relatively poorly understood.Thus, highlighting this ion is a challenging task that could be useful to rationalize the stereochemical outcome of glycosylation reactions. Furthermore, the data associated with this ion could be exploited to improve the synthesis of oligosaccharides and glycoconjugates. Several research groups mainly based in the US and Japan are involved in the quest for the oxycarbenium ion using various approaches. In addition, the exceedingly short life of non-stabilized glycosyl cations in organic solution makes their delicate direct observation.The aim of the project presented in this report is based on the use two chemistries: glycochemistry and superacid and two analytical techniques by low-temperature NMR assisted by computational study to generate, identify and fully characterize the glycosyl cations. After generating transient species in superacid media, the long-lived intermediates as the known dioxalenium and oxazolinium ions are studied by in situ NMR. From peracetylated 2-deoxy and 2-bromoglucopyranose, the glycosyl cation is generated and deeply analysed for the first time in a condensed phase. NMR aided by complementary computations predicts the privileged three-dimensional structural for each intermediate. The trapping by even poor nucleophile further confirms the impact of the structure of the glycosyl cation on the stereochemical outcome.

Submitted by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2018-04-20T13:07:11Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertação Jucilene Lopes.pdf: 2211418 bytes, checksum: 953a473330915d500a4941021f07c45c (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2018-04-20T13:08:40Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertação Jucilene Lopes.pdf: 2211418 bytes, checksum: 953a473330915d500a4941021f07c45c (MD5) / Made available in DSpace on 2018-04-20T13:08:40Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertação Jucilene Lopes.pdf: 2211418 bytes, checksum: 953a473330915d500a4941021f07c45c (MD5) Previous issue date: 2017-10-30 / FAPEAM - Fundação de Amparo à Pesquisa do Estado do Amazonas / Metallic sulfates when used to modify acidic solids have conferred an increase in the acidity of the acidic sites of Lewis and Brønsted, presenting Hammett acidity constant superior to that of sulfuric acid, being called superacid materials. For this reason, superacid materials have been developed and used in many catalytic reactions. In this work the nickel sulfate (NiSO4) and metakaolinite obtained from the kaolinite soil of Manaus - AM were used to synthesize superacid materials varying NiSO4 concentration and calcination temperature. The materials were characterized by chemical analysis (FRX), thermogravimetry (TGA), Infrared Spectroscopy with Fourier Transform (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), adsorption-desorption of N2 (BET method) and still the acidity of the materials was studied by infrared spectroscopy technique of adsorbed pyridine. The catalytic activity was investigated by photodegradation of methylene blue. The characterization results showed that the addition of sulfate ions on the surface of metakaolinite did not alter the structure and morphology of the catalytic support. Bands relative to Lewis acid sites were observed at 1445 and 1607 cm -1 and Brønsted at approximately 1638 cm -1. The metakaolinite sample showed a 43.2% degradation of methylene blue, presenting better performance among all samples tested. Therefore, the characterization of the materials showed that there was interaction between the nickel sulfate and the catalytic support, resulting in the obtaining of the superacid materials and also the addition of nickel sulfate in the catalytic support caused some modification in the surface acidity of metakaolinite. However, the catalytic tests showed that the superacid materials had little catalytic activity for methylene blue photodegradation reactions. / Sulfatos metálicos quando utilizados para modificar sólidos ácidos tem conferido um aumento na acidez dos sítios ácidos de Lewis e Brønsted, apresentando constante de acidez de Hammett superior ao do ácido sulfúrico, sendo chamados de materiais superácidos. Por esse motivo, materiais superácidos têm sido desenvolvidos e utilizados em muitas reações catalíticas. Nesse trabalho o sulfato de níquel (NiSO4) e metacaulinita obtida de solo caulinitico de Manaus – AM, foram utilizados para sintetizar materiais superácidos variando concentração de NiSO4 e temperatura de calcinação. Os materiais obtidos foram caracterizados por meio de análise química (FRX), termogravimetria (TGA), infravermelho com transformada de Fourier (FTIR), difração de raios X (DRX), microscopia eletrônica de varredura (MEV), adsorção-desorção de N2 (método BET) e ainda a acidez dos materiais foram estudadas por meio da técnica de espectroscopia na região do infravermelho de piridina adsorvida. A atividade catalítica foi investigada por meio da fotodegradação do azul de metileno. Os resultados de caracterização mostraram que a adição de íons sulfatos na superfície da metacaulinita não alterar a estrutura e morfologia do suporte catalítico. As bandas referentes aos sítios ácidos de Lewis foram observadas em 1445 e 1607 cm-1 e de Brønsted em aproximadamente 1638 cm–1. A amostra de metacaulinita apresentou 43,2% de degradação do azul de metileno, apresentando melhor desempenho entre todas as amostras testadas. Portanto, a caracterização dos materiais demonstrou que houve interação entre o sulfato de níquel e o suporte catalítico, resultando na obtenção dos materiais superácidos e ainda a adição de sulfato de níquel no suporte catalítico causou alguma modificação na acidez superficial da metacaulinita. Porém, os testes fotocatalíticos demonstraram que os materiais superácidos apresentaram pouca atividade catalítica para reações de fotodegradação do azul de metileno.

Le biogaz est une source d’énergie qui intéresse de plus en plus l’Europe et notamment la France pour ses avantages environnementaux et économiques. Produit de la fermentation de matière organique, il contient du biométhane. Ce dernier est une alternative plus durable aux énergies fossiles. Cependant, à l’état brut, les polluants dans le biogaz peuvent provoquer des dégâts sur la santé et l’environnement, notamment en raison de la présence de siloxanes et des composés soufrés. L’objectif de cette recherche consiste donc à développer des méthodes améliorant à la fois économiquement et écologiquement la désulfuration du biogaz, dans le but de les intégrer aux unités de traitement du biogaz déjà existantes et présentes sur le territoire. A partir d’un état de l’art sur les propriétés du biogaz et ses traitements de purification, deux procédés ont été particulièrement mis en avant et étudiés dans cette thèse. Le premier correspond au traitement de la désulfuration en précombustion consistant à éliminer le H2S et les siloxanes à travers un réacteur polyphasé à barbotage gaz-liquide spécifique, utilisant un nouveau solvant avec des propriétés « superacides ». Le second, quant à lui, correspond au traitement en postcombustion de la désulfuration des fumées provenant de la combustion du gaz, via un réacteur polyphasé à lit fixe gaz-solide. Pour ce faire, un prototype de l’unité de désulfuration est intégralement conçu, construit et testé dans le cadre de la thèse. Cette thèse présente notamment le développement des différents modèles numériques, ainsi que les résultats d’expériences en laboratoire, confirmant l’efficacité de ces procédés innovants. / Biogas. It is an energy source increasingly popular in Europe, remarkably in France, due to its environmental-friendly and economic-saving capabilities. It is produced by the organic matter fermentation, leading to biomethane production, as a sustainable alternative to fossil fuels. Nevertheless, as a raw gas, pollutants in biogas lead to environmental, health and process-related issues, especially because of its unique content on sulfur compounds. The objective of this research is to develop new processes, economically and environmentally feasible, for biogas desulfurization, seeking a process integration in existing biogas treatment units in France. Considering the state of the art on biogas properties and its possible purification treatments, two processes have been identified and studied in this thesis. The first process is a precombustion desulfurization treatment aiming to eliminate the H2S and the siloxanes through a gas-liquid bubbling-typed polyphasic reactor. This reactor is equipped with a new solvent with “superacid” properties. The second process is a postcombution desulfurization treatment for stack gas, through a gas-solid fixed-bed polyphasic reactor. A prototype of this unit was entirely designed, built and tested in the thesis. This thesis describes the applied research method, the developed numerical models, and the experimental results confirming the efficiency of the novel processes.

No description available.

Grâce à leurs fortes acidités, les milieux superacides permettent d’accéder par polyprotonation à des intermédiaires superélectrophiles polycationiques, capables d’être piégés par des nucléophiles très faibles. Ces espèces très réactives ont permis de développer des méthodologies de synthèse sans équivalent en conditions « classiques ».Dans la première partie de ce travail, le comportement de composés organophosphorés dans le milieu HF/SbF5 a été évalué et les sites de protonation de différentes fonctions phosphorées ont pu être observés par RMN in situ à basse température. La réactivité d’oxydes de phosphines insaturés a également été évaluée et des composés organophosphorés cycliques et/ou fluorés ont été synthétisés avec de bons rendements. Des expériences de RMN in situ à basse température ont permis de mettre en évidence un intermédiaire superélectrophile de type phosphonium-carbénium inédit dont l’implication a été confirmée par des calculs théoriques.La deuxième partie est consacrée à l’exploitation de la contrainte benzylique d’espèces superélectrophiles. A partir d’éphédrines tosylées, des benzosultames cycliques ont été obtenus par cyclisation intramoléculaire diastéréospécifique dans l’acide trifluorométhanesulfonique. L’analyse des intermédiaires réactionnels par RMN a permis de révéler l’implication d’une contrainte benzylique contrôlant la spécificité de la réaction. Les benzosultames chiraux N-F obtenus après fluoration ont été utilisés comme réactifs de fluoration électrophile énantiosélective et la synthèse de dioxydes de méthanodibenzothiazocines chiraux inédits a également été envisagée. / Thanks to their exceptional acidity, superacid allow access to polycationic superelectrophiles by polyprotonation. These highly reactive species are capable of being trapped by very weak nucleophiles and can be used to develop new synthetic methodologies without equivalents under “classical” conditions. In the first part of this work, the behavior of organophosphorus compounds in HF/SbF5 was evaluated and the protonation sites of different phosphorus functions have been observed by low temperature NMR spectroscopy. The reactivity of unsaturated phosphine oxides has also been evaluated and cyclic and/or fluorinated organophosphorus compounds have been synthetized in good yields. In situ low-temperature NMR experiments revealed a phosphonium-carbenium superelectrophilic intermediate whose implication was confirmed by theoretical calculations. The second part deals with the study of the benzylic strain applied to superelectrophilic species. From tosylated ephedrines, cyclic benzosultams were obtained by diastereospecific intramolecular process in trifluoromethanesulfonic acid. Analysis of the reaction intermediates by NMR revealed the implication of a benzylic strain controlling the specificity of the reaction. After fluorination, the obtained N-F chiral benzosultams were used as enantioselective electrophilic fluorination reagents and the synthesis of new chiral methanodibenzothiazocine dioxides was also considered.