As zeólitas são amplamente utilizadas pela indústria em diferentes processos. Nos processos relacionados à conversão térmica do carvão, as zeólitas encontram aplicação, por exemplo, como suporte de catalisadores para a Síntese de Fischer-Tropsch, ou mesmo como adsorventes de efluentes líquidos ou de gases poluentes. No entanto, a microporosidade da zeólita limita a difusão dos produtos e dos reagentes ocasionando um transporte de massa lento e um longo tempo de residência, aumentando a possibilidade de reações secundárias, formação de coque e desativação do catalisador. Uma das maneiras de superar essas limitações é a introdução de um sistema secundário de poros, através da reestruturação da rede cristalina com modeladores de estruturas ou ataques químicos básicos e ácidos nas zeólitas de modo a formar materiais hierárquicos ou mesoporosos. Neste trabalho, foram investigadas três rotas para promover a mesoporosidade em zeólitas do tipo Y. Primeiramente foi realizada a síntese da zeólita hierárquica através da modificação com líquidos iônicos. O segundo método empregado foi o processo de dessilicação, utilizando hidróxido de sódio como base e, por último, a desaluminação com ácido oxálico. As zeólitas mesoporosas foram caracterizadas através de análises de área específica (BET), distribuição de tamanho de poros (BJH), difração de raios X (DRX) e redução à temperatura programada (TPR-H2). Dentre os métodos adotados, os resultados para DRX e BET mostraram que o tratamento de dessilicação destruiu a cristalinidade da zeólita, acarretando no abandono dessa rota de investigação. A síntese com líquido iônico se mostrou eficiente para a formação de mesoporos e, conforme a distribuição de tamanho de poros, seu sistema apresentou-se ordenado de maneira hierarquizada. A desaluminação não danificou a estrutura da zeólita, porém foi obtido um aumento pouco expressivo em seu número de mesoporos. A reação de esterificação foi utilizada, como modelo, para avaliar o efeito dos mesoporos sobre a atividade catalítica da reação. A reação de esterificação ocorreu a 70°C por 1 h, utilizando ácido acético e álcoois com diferentes tamanhos de moléculas. Em comparação à zeólita de partida (CBV720 - Zeolyst), a criação da mesoporosidade na zeólita através dos líquidos iônicos resultou em um aumentou na conversão de ácido acético para os álcoois etílico (em 17,65%), isopropílico (em 8,42%) e isobutílico (em 2%). Para a zeólita mesoporosa sintetizada por desaluminação, houve um acréscimo de 10,93% e 2,11% na conversão para os álcoois etílico e isopropílico, respectivamente. Os resultados mostraram que a presença de mesoporosidade influenciou positivamente o desempenho das zeólitas Y na reação modelo de esterificação, mostrando-se um excelente mecanismo a ser aplicado para facilitar o transporte de massa nos poros da zeólita, especialmente para a síntese feita com o emprego de líquidos iônicos. / Zeolites are widely used by industry in different processes. In processes related to the thermal conversion of coal, the zeolites find application, for example, as catalyst support for the Fischer-Tropsch Synthesis, or even as adsorbents of liquid effluents or pollutant gases. However, the small pore diameter of the zeolite limits the diffusion of the products and the reactants causing slow mass transport and a long residence time that increase the possibility of secondary reactions, coke formation and catalyst deactivation. One of the ways to overcome these limitations is the introduction of a secondary pore system by restructuring the crystal lattice with structural modellers or basic chemical and acidic attacks on zeolites to form hierarchical or mesoporous materials. In this work, three routes were investigated to promote mesoporosity in Y type zeolites. First, the hierarchical zeolite was synthesized through the modification with ionic liquids. The second method used was the desilication process, using sodium hydroxide as the base and, finally, the desalumination method with oxalic acid. The mesoporous zeolites were characterized by specific surface area analysis (BET), pore size distribution (BJH), X-ray diffraction (XRD) and temperature programmed reduction (TPR-H2). Among the methods adopted, the results for XRD and BET showed that the desilication treatment destroyed the crystallinity of the zeolite, leading to the abandonment of this research route. The synthesis with ionic liquid was efficient for the formation of mesopores and, according to the pore size distribution, its system was hierarchically ordered. The desalumination did not damage the zeolite structure, but a small increase in its number of mesopores was noted. The esterification reaction was used to evaluate the effect of mesopores on the catalytic activityof the reaction. The esterification reaction occurred at 70°C for 1 h using acetic acid and alcohols with different sizes of molecules. Compared to the starting zeolite (CBV720 - Zeolyst), the creation of mesoporosity in the zeolite through the ionic liquids resulted in an increase in the conversion of acetic acid for the reaction conducted with ethyl (17.65%), isopropyl (8.42%) and isobutyl alcohols (2%). For the mesoporous zeolite synthesized by desalumination, there was an increase of 10.93% and 2.11% in the conversion to the ethyl and isopropyl alcohols, respectively. The results showed that the presence of mesoporosity positively influenced the performance of the zeolites Y in the esterification model reaction, showing an excellent mechanism to be applied to facilitate the mass transport in the zeolite pores, especially for the synthesis made with the use of ionic liquids.

Orientador: Paulo José Samenho Moran / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T16:43:49Z (GMT). No. of bitstreams: 1 Paula_BrunoRicardoSilvade_M.pdf: 10291593 bytes, checksum: c054e04292035c00a7e70ac53eea2231 (MD5) Previous issue date: 2012 / Resumo: Nesse projeto investigou-se o uso de líquidos iônicos na preparação de compostos carbonílicos a,b-insaturados por meio da condensação de Knoevenagel e na biorredução dos produtos sintetizados. Na primeira etapa do projeto, estudou-se a aplicação de um protocolo desenvolvido pelo grupo de pesquisa para a condensação de Knoevenagel entre b-cetoésteres e aldeídos aromáticos em líquidos iônicos. Utilizaram-se os líquidos iônicos [bmim(PF6)] e [bmim(NTf2)], e em ambos os casos, obtiveram-se rendimentos de moderado a alto para as condensações envolvendo o acetoacetato de etila e o 4-cloroacetoacetato de etila. Os produtos obtidos, que em todos os casos foram misturas de diastereoisômeros, foram separados e caracterizados individualmente, e a configurações das olefinas (E ou Z) puderam ser determinadas com base na cristalografia de raios-X de dois dos compostos preparados, e posterior comparação dos espectros de RMN de C de todos os compostos sintetizados. O acetoacetato de etila forneceu como isômero majoritário o Z, enquanto o 4-cloroacetoacetato de etila forneceu como isômero majoritário o E. Na segunda etapa do projeto, estudaram-se as biorreduções dos compostos preparados em sistemas bifásicos água/líquido iônico hidrofóbico. Em geral, verificou-se que na biorredução dos derivados do acetoacetato de etila por Saccharomyces cerevisiae, a existência de um sistema bifásico fez com que houvesse a redução da olefina, mantendo a carbonila intacta, enquanto no sistema monofásico (aquoso) houve a redução tanto da olefina quanto da carbonila. O comportamento da reação de biorredução foi bastante sensível a natureza do anel aromático, sendo que em alguns casos os produtos de retro-Knoevenagel foram formados em quantidades significativas. No caso do 2-benzilidenoacetoacetato de etila, pôde-se verificar que um comportamento semelhante foi observado em termos de quimiosseletividade para a redução dos derivados do acetoacetato de etila na presença de uma resina acrílica (Amberlite XAD-7). No caso dos derivados do 4-cloroacetoacetato de etila, as biorreduções por Saccharomyces cerevisiae, Saccharomyces boulardii, Candida albicans, Pichia stipitis e Geotrichum candidum forneceram como majoritários os produtos de retro-Knoevenagel. No caso da biorredução por Rhodotorula glutinis, houve apenas um aumento do tempo de reação, com manutenção da redução dos dois grupos funcionais / Abstract: In this project, we studied the use of ionic liquids in the preparation of a,b-unsaturated compounds by the Knoevenagel condensation, and in their bioreductions by yeasts. In the first stage, a methodology developed by our research group for the a-methylenation of carbonyl compounds in ionic liquids was applied to the condensation of b-ketoesters and aromatic aldehydes. In condensations involving ethyl acetoacetate and 4-chloroacetoacetate, moderate to high yields were obtained using [bmim(PF6)] and [bmim(NTf2)]. In all cases, diastereomeric mixtures were obtained, and both isomers were separated and characterized individually. The determination of the olefin configuration was based on X-ray crystallography of two of the synthesized compounds, and further comparison of their C NMR spectra with those of the remaining products. Although the reactions proceeded with only low to moderate diastereoselectivity, it was noteworthy that, whereas ethyl acetoacetate favored the Z isomer as the major reaction product, ethyl 4-chloroacetoacetate favored the E isomer as the major one. In the second stage, the bioreductions of the synthetized compounds in water/[bmim(PF6)] were studied. For the reduction of ethyl 2-benzylideneacetoacetate by Saccharomyces cerevisiae, the use of a water/[bmim(PF6)] system resulted in the maintenance of the C=O bond, with reduction only of the C=C bond. In contrast, in water, both the C=O and C=C bonds are reduced. When other acetoacetate derivatives were employed, it was noted that both reaction rates and the byproducts varied greatly varying the aromatic ring. When the reaction was performed in a aqueous system with the substrate adsorbed in an acrylic resin (Amberlite XAD-7), a similar result in terms of chemoselectivity was observed. When reductions of ethyl 2-benzylidene-4-chloroacetoacetate were carried out with Saccharomyces cerevisiae, Saccharomyces boulardii, Candida albicans, Pichia stipitis and Geotrichum candidum, the major observed products were those of a retro-Knoevenagel reaction. Only when Rhodotorula glutinis was employed, the major products were the bioreduction ones. In this case, however, the use of a water/[bmim(PF6)] system only resulted in a decrease of both C=O and C=C reduction rates, but not in a favoring of C=C reduction / Mestrado / Quimica Organica / Mestre em Química

Les nanoparticules (NPs) métalliques possèdent des propriétés physiques inhabituelles et suscitent un grand intérêt pour divers domaines d’application. En particulier, les NPs de métaux magnétiques offrent de nombreux avantages dans une grande variété d’applications technologiques, médicales et en catalyse. Généralement, ces applications nécessitent de fabriquer des NPs de taille et de composition contrôlées. Cette thèse vise à démontrer que de telles NPs peuvent être obtenues par décomposition de précurseurs organométalliques (OM) dans des solvants d’un genre particulier, les liquides ioniques (LIs). Ce sont des sels possédant un très bas point de fusion (inférieur à 100°C) et qui possèdent des propriétés uniques, dont celle de stabiliser des nano-objets. Pour y parvenir, des précurseurs OM des métaux d’intérêt (Co et Fe) ont été identifiés. Des Co-NPs ont pu être synthétisées de manière contrôlée : elles possèdent une structure cristalline du e-Co et les propriétés superparamagnétiques attendues pour le Co(0). Dans le cas du Fe, une oxydation partielle des NPs n’a pu être évitée. La seconde partie du travail s’est donc concentrée sur l’obtention de NPs bimétalliques CoM, avec M=Ru ou Pt. Dans le cas de Ru, toutes les synthèses ont conduit à des NPs bimétalliques, tandis que seule une décomposition simultanée des deux précurseurs de Co et Pt a permis de former des CoPt-NPs. Ces NPs pourraient permettre de fabriquer des dispositifs de stockage de données plus performants ou des catalyseurs moins onéreux / Metallic nanoparticles (NPs) exhibit unique physical and chemical properties. However, their use is conditioned by the ability to control their size and structure. The decomposition of organometallic (OM) precursors under H2 is efficient to generate metallic NPs in organic solvents, but also in ionic liquids (ILs). We have shown that in the latter media, the size can be finely tuned without adding stabilizing agents. Moreover, the resulting “naked” metallic NPs are suitable for catalysis or further reaction with a second OM precursor to form bimetallic NPs.In this work, we applied this knowledge to the synthesis of mono- and bimetallic NPs in imidazolium-based ILs C1CaImNTf2. CoNPs with a diameter of ca. 4 nm were successfully synthesized by decomposition of [Co(?3-C8H13)(?4-C8H12)] under H2. Structural analysis and magnetic characterizations demonstrated that these NPs are metallic and, as expected for this size, superparamagnetic. This approach was extended to the synthesis of bimetallic CoPt and CoRu NPs. It turned out that the best strategy is probably to simultaneously decompose the Co and Pt (or Ru) precursors. This reaction provides monodisperse suspensions of NPs, a good indication that they are bimetallic. Further structural characterizations, in particular using anomalous SAXS, are also considered to elucidate their structure

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17525号 / 工博第3684号 / 新制||工||1560(附属図書館) / 30291 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 啓文, 教授 今堀 博, 教授 山本 量一 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17587号 / 工博第3746号 / 新制||工||1571(附属図書館) / 30353 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 陰山 洋, 教授 阿部 竜 / 学位規則第4条第1項該当

Orientador: Maria Regina Wolf Maciel / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-18T13:50:07Z (GMT). No. of bitstreams: 1 JaimesFigueroa_JaiverEfren_M.pdf: 4284661 bytes, checksum: 5b7383def90a5143160bc892b406c75c (MD5) Previous issue date: 2011 / Resumo: A produção de etanol a partir da cana de açúcar é uma tecnologia dominada completamente pelo Brasil porém, encontra-se na etapa de intensificação, otimização e inovação. O etanol pode ser produzido como hidratado ou anidro, sendo necessário, para produção deste último, um processo posterior de desidratação. Existem inúmeros processos de desidratação, dentre dos quais a destilação extrativa é um dos mais simples de realizar. A destilação extrativa usa um solvente para modificar o equilíbrio líquido-vapor, permitindo quebrar o azeótropo etanol/água que impede que a desidratação seja feita por destilação convencional. O solvente de extração é de grande importância, dele depende a facilidade com que vai ser feita a separação, a quantidade a ser utilizada e o requerimento energético do processo. Nesse contexto, aparecem os líquidos iônicos, que são apresentados como ótimos solventes potenciais de extração; um líquido iônico (LI) é um sal composto por um cátion orgânico com pelo menos uma carga deslocada e um ânion inorgânico; sua estrutura evita que se forme uma rede cristalina estável, resultando em solventes líquidos altamente iônicos com temperaturas de fusão inferiores a 100 °C e com insignificante pressão de vapor. Os LI são principalmente usados em substituição aos solventes convencionais, podendo ser uma alternativa para diminuir a poluição ambiental, evitando a emissão de componentes orgânicos voláteis ao meio ambiente. Com a justificativa anterior, o objetivo desta dissertação foi analisar e otimizar o processo de obtenção de etanol anidro a partir da mistura etanol + água de composição pré-azeotrópica, empregando líquidos iônicos (LI), visando avaliar seu potencial; os LI estudados foram: 1-butil-3-metilimidazólio cloreto, 1-butil-3-metilimidazólio metilsulfato, 1-butil-3-metilimidazólio acetato, 1-butil-3-metilimidazólio tetrafluoroborato, 1-butil-3-metilimidazólio dicianamida, 1-etil-3-metilimidazólio cloreto, 1-etil-3-metilimidazólio tetrafluoroborato, 1-hexil-3-metilimidazólio cloreto. Neste trabalho foi encontrado o requerimento energético e a quantidade de LI a ser empregado para obter os valores máximos de pureza e porcentagens de recuperação de etanol e água. A influência das condições de operação e desenho utilizadas, tais como fração de etanol na alimentação, relação LI:alimentação, temperatura da alimentação e do LI de reposição, quantidade de estágios, relação molar de refluxo, estágio de alimentação e vazão molar de destilado da coluna de recuperação de etanol e de purificação de LI, foram analisadas empregando o simulador comercial Aspen Plus e, otimizadas empregando a técnica de delineamento de experimentos. Todos os LI estudados apresentaram capacidade de desidratar o etanol, elevando sua concentração de pré até pós-azeotropia, obtendo-se pureza de etanol maiores que 0,995 em massa. Além disso, dependendo do LI utilizado, o processo atinge porcentagens de recuperação de etanol e água, em média, de 98% e 74%, respectivamente. Na definição do modelo para o coeficiente de atividade do equilíbrio ternário líquido vapor da mistura etanol + água + LI foram testados o NRTL e UNIQUAC, chegando-se à conclusão de que o equilíbrio representado pelo modelo de NRTL é o mais adequado / Abstract: The production of ethanol from sugar cane is a technology led and dominated by Brazil. However, it is still in a stage of optimization and innovation. Ethanol can be produced in a hydrated or dehydrated state, but the latter requires an additional process to the conventional distillation. There are numerous dehydration processes that can be implemented, but the extractive distillation is one of the most simple. Extractive distillation uses a solvent that modifies the liquid-vapor equilibrium and eliminates the presence of the ethanol-water azeotrope that prevents the use of conventional distillation for the dehydration process. The solvent for the extraction is of great importance since it dictates the degree of separation and the energy requirements for the process. In this context, ionic liquids are considered since they have been presented as excellent solvents for extraction. An ionic liquid (IL) is a salt formed by an organic cation with at least one delocalized charge, and an inorganic anion. The structure of the ionic liquids prevents the formation of a stable crystalline net, resulting in highly ionic liquid solvents that have melting points below 100 ºC and negligible vapor pressures. With those characteristics, ionic liquids can be a replacement for conventional solvents offering alternatives for the decrease of the environmental impact by preventing the emissions of volatile compounds to the environment. With the previous justification, the objective of this master dissertation was to analyze and optimize the process of obtaining anhydrous ethanol from a mixture ethanol + water with pre-azeotropic composition by using ionic liquids; and also to evaluate their performance in this application to evaluate its potential. Ionic liquids were studied: 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexil-3-methylimidazolium chloride. In this work, the minimum energy requirement and the amount of ionic liquid needed to obtain maximum ethanol purity and maximum recovery of ethanol and water exiting the process were found. The influence of the design and operation conditions used, such as the ethanol composition in the feed, the IL/feed ratio, the temperature of the feed and the IL, the number of plates, the reflux molar ratio and the distilled flux in the columns of purification of ethanol and recovery of ionic liquids were studied using the commercial simulator ASPEN PLUS, and optimized by utilization of the design of experiments (DOE) technique. All the ionic liquids used were able to dehydrate the ethanol, increasing its concentration from pre to post azeotrope, generating ethanol with purity above 0.995 in mass. In addition to that, depending on the ionic liquid used, the process reached average water and ethanol recoveries of 98% and 74% respectively. In the definition of the model for the activity coefficient in the ternary vapor-liquid equilibrium of the ethanol-water-IL mixtures, the models NRTL and UNIQUAC were studied concluding that the NRTL model was the most adequate / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

In this dissertation, three aspects about surface and interface engineering of conjugated polymers and nanomaterials will be discussed. (i) There is a significant promise for electroactive conjugated polymers (ECPs) in applications of electrochemical devices including energy harvesting, electrochromic displays, etc. Among these, ECPs has also been developed as electroactive materials in electrochemical supercapacitors (ESCs). Compared with metal oxides, ECPs are attractive because they have good intrinsic conductivity, low band-gaps, relatively fast doping-and-undoping process, the ease of synthesis, and tunable electronic and structural properties through structural modifications. Here, Multiple-branch-chain 3,4-ethylenedioxythiophene (EDOT) derivatives was designed as crosslinkers in the co-electropolymerization of EDOT to optimize its morphology and improve the cycling stability of PEDOT in the supercapacitor applications. High-surface-area π-conjugated polymeric networks can be synthesized via the electrochemical copolymerization of the 2D (trivalent) motifs benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (BTT) and tris-EDOT-benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (TEBTT) with EDOT. Of all the material systems studied, P(TEBTT/EDOT)-based frameworks achieved the highest areal capacitance with values as high as 443.8 mF cm-2 (at 1 mA cm-2), higher than those achieved by the respective homopolymers (PTEBTT and PEDOT) in the same experimental conditions of electrodeposition (PTEBTT: 271.1 mF cm-2 (at 1 mA cm-2); PEDOT: 12.1 mF cm-2 (at 1 mA cm-2). (ii) In electrochemical process, the suitable choice of appropriate electrolytes to enlarge the safe working potential window with electrolyte stability is well known to improve ECPs’ performance in ESCs applications. Ionic liquids (ILs) are ion-composed salts and usually fluid within a wide temperature range with low melting points. There are many unique characteristics for these intrinsic ion conductors, including high ionic conductivity, wide electrochemical voltage windows in neutral conditions, fast ion mobility in redox reaction process (>10-14 m2 V-1 s-1), low vapor pressure, and environmental stability. These properties qualified ambient-temperature ILs to be applied as supporting medium for various devices and materials processing applications in both industry and academia, overcoming the limitation of volatile organic compounds (VOCs). Especially, ILs have been utilized as superior medium to electrodeposit metals, alloys, semiconductors and ECPs in the application of supercapacitors. Electropolymerization of EDOT and its derivative 4,4'-dimethoxy-3,3'-bithiophene (BEDOT) have been studied in three kinds of imidazolium-based ionic liquids and conducting salt in VOCs with different anions both as the growth medium and the supporting electrolyte, to assess the influence of these anions on their morphology and electrochemical activity. It is found these thiophene polymers grown in ILs with higher viscosity and lower diffusion shows much slower growth rate and orderly morphologies than in Tetrabutylammonium hexafluorophosphate (TBAPF6) dissolved in acetonitrile (ACN), and gives better electrochemical performance via cyclic voltammetry (CV) and galvanostatic charge-and-discharge (CD) studies. Polymers displayed multiple redox peaks in several cases, the possible reasons and origins are discussed. The synthesized polymer can be affected greatly by both the ILs with different anion/cation, and its mutal interation with targeted monomer.. As far as known, there is no systematic study on how the anions of ILs and common organic solution could play a role as a medium both for polymerization and post-polymerization electrolyte for PEDOT and its derivatives. This study can be used as an easy reference and provide experimental diagnositc data when selecting ionic liquids to investigate and optimize thiophene-based electrochemical systems, such as batteries and supercapactiors. (iii) Another aspect about interface chemistry of direct functionalization of nanodiamond with maleimide has also been addressed. Functional nanodiamonds are promising candidates for extensive practical applications in surface science, photonics and nanomedicine. Here, a protocol of direct functionalization is described by which maleimide-derivatized substituents can be appended to the outer shell of thermally annealed nanodiamonds through Diels-Alder reaction. This protocol can be carried out in room temperature, ambient atmosphere, without catalyst, and provide functionalized nanodiamonds with good solubility in organic solution. Also, this method can be applied for other maleimide derivatives,e.g.m aleimide-fluorescene, which can be applied in fluorescence labeling, sensing, and drug delivery. A series of techniques, especially Fourier transform infrared spectroscopy (FTIR), and Solid State Nuclear Magnetic Resonance (SS-NMR) was conducted for the analysis of surface chemistry and the investigation of the two-point binding strategy in details.

No description available.

No description available.

No description available.