Over the last 100 years there has been an increase of greenhouse gases (CO2, CH4 and N2O) in the atmosphere. These gases cause several problems with the climate on Earth, such as increasing problems with extreme weather. One way to decrease the outlet of carbon dioxide is by adsorption and capture of CO2. Biobased aerogels are one way to adsorb CO2. In this project the goal is to increase the CO2 adsorption capacity of a biobased carbon aerogel with zeolite nanoplates. The biobased carbon aerogel is prepared via freeze-casting a suspension made of LignoBoost lignin and (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidized cellulose nanofibers, also called TEMPO-cellulose nanofibers (TOCNF). The freeze-casted structure is, after freeze-drying and carbonization, decorated with zeolite nanoplates. To find the optimal decorating method, three different decoration methods were tested. Thesemethods are called “decoration assisted by cationic polymer solution” (DC), “direct decoration” (DD) and “decoration incorporated directly in lignin suspension” (DS). The X-ray diffraction (XRD) together with Energy-dispersive X-ray spectroscopy (EDX), showed that the highest concentration of zeolite nanoplates in the samples, was achieved by the “decoration incorporated directly in lignin suspension” method. CO2 adsorption capacity test was performed at temperatures of 273.150K, 298.150K and 323.150K. The DS-sample did not perform better than the reference sample at low pressures (10kPa). At higher pressure (100kPa) the DS-sample had the highest adsorption capacity at test temperatures 273.150K and 323.150K.

This thesis, which comprises of a theoretical and a practical part, deals with possible means of increasing ceramic body frost resistance. The current state of research in the field of ceramic body frost resistance is summarized in the theoretical part. The practical part is divided into two sections. In the first section, the influence of firing temperature (820 °C and 1020 °C) and duration (2, 4 and 6 hours) on frost resistance and several other parameters is assessed by means of experiment, using a specimen of brick body made of mixes currently used in roof tile production by TONDACH Šlapanice and TONDACH Dolní Jirčany factories. In the second section of the practical part, two modifications are introduced of the mixture currently used in roof tile production in the TONDACH Šlapanice factory – GE clay and zeolite supplements were added, the effects of which are verified by means of experiment using specimens fired in a kiln designated for ceramic masonry blocks and alternatively in a kiln used for firing TONDACH Šlapanice roof tiles.

This master thesis deals with the filtration of air contaminated with oil and the total efficiency and propose a new filtration system. The reason is insufficient capacity and functionality of the operating device is incorrect. It will propose the most appropriate solution to this in terms of economic and technical design is satisfactory.

Cette étude est centrée sur la synthèse et la préparation de zéolithes modifiées par des métaux de transition avec leurs applications en catalyse sous irradiation microondes. Des travaux précédents ont montré l’intérêt de modifier des zéolithes avec des métaux de transition pour leur application sur des réactions d’oxydation et d’utiliser les microondes afin d’augmenter les vitesses de réaction. Dans cette thèse, nous avons étudié deux types de structure zéolithique (MEL et FAU) dopés par des métaux de transition (Co, Mn, Fe, Zn, Ni, Cr) à différentes concentrations. Une étude classique de caractérisation a permis d’augmenter la connaissance sur la préparation de zéolithes modifiées et de comprendre leur influence sur l’activité catalytique. La réaction d’oxydation partielle du styrène pour la production du benzaldéhyde a été choisie comme réaction modèle. La zéolithe Co-ZSM-11 a présenté la meilleure activité catalytique dans cette étude ainsi que par rapport à d’autres catalyseurs présentés dans la littérature.Les réactions d’oxydation du styrène ont été étudiées sous irradiation microondes et sous chauffage conventionnel. Aucune différence sur l’activité des zéolithes dopées n’a été observée pour les deux types de chauffage. Les faibles valeurs de permittivités et perméabilités des zéolithes dopées par des métaux de transition rendent difficile l’intensification du procédé d’obtention de benzaldéhyde à partir de l’oxydation du styrène sous microondes. Les paramètres de la réaction modèle ont été optimisés et une étude cinétique a été menée avec la zéolithe Co-ZSM-11. Enfin, le chauffage par hystérésis diélectrique a été utilisé dans la synthèse de zéolithes ZSM-11. Le temps de synthèse a été considérablement réduit (80%) par rapport au temps nécessaire sous chauffage conventionnel. / This study focuses on the synthesis and preparation of modified zeolites with transition metals and theirs applications in catalysis under microwave irradiation. Previous works have shown interest in modifying zeolites with transition metals for their application to oxidation reactions and in using microwave irradiation in order to increase the reaction rates. In this thesis, we studied two types of zeolite structure (MEL and FAU) doped with transitionmetals (Co, Mn, Fe, Zn, Ni, Cr) at different concentrations. A classic characterization study has increased the knowledge on the preparation of modified zeolites and the understanding of their influence on thecatalytic activity. The styrene partial oxidation reaction for benzaldehyde production was chosen as amodel reaction. Co-ZSM-11 zeolite presented the best catalytic activity in this study and also compared to other catalysts found in the literature. The styrene oxidation reactions were studied under microwave irradiation and under conventional heating. No difference in the activity of doped zeolites was observed for both types of heating. The low values of permittivity and permeability of zeolites doped with transition metals make difficult the intensification of the benzaldehyde production process from styrene oxidation under microwave. The parameters of the model reaction have been optimized and a reaction kinetic study was carried out by using the Co-ZSM-11 zeolite. Finally, the hysteresis dielectric heating was used in the synthesis of ZSM-11. The synthesis time was significantly reduced (80%) under microwave irradiation compared to conventional heating.

Orientador: Fauze Ahmad Aouada / Resumo: Com o objetivo de aplicar agroquímicos de uma forma controlada, e reduzir os danos à saúde e ao meio ambiente causados por estes, foram desenvolvidos neste trabalho, dois novos hidrogéis a partir de dois polissacarídeos diferentes carboximetilcelulose (CMC) e quitosana (Qs), suportados em redes de poli (ácido metacrílico)-co-poliacrilamida (PMAA-co-PAAm). Também foi investigada a influência da zeólita nas principais propriedades agroquímicas desses materiais como sorção e dessorção de herbicidas. A estabilidade da zeólita na solução polimérica foi estudada por meio de medidas de viscosidade. Estes comprovaram que a adição de polissacarídeo na solução formadora dos hidrogéis possibilita a obtenção de um hidrogel nanocompósito homogêneo. A incorporação da zeólita nos hidrogéis foi confirmada pela presença das bandas características da zeólita em 798 cm-1 e 600 cm-1 nos espectros de FTIR dos hidrogéis nanoestruturados. Outros indícios de incorporação foram a redução no volume dos poros e a presença de microporos nas paredes dos poros dos hidrogéis, aumento na massa residual dos hidrogéis nanoestruturados a 800ºC, observados nos resultados obtidos por microscopia eletrônica de varredura (MEV) e análise termogravimétrica (TG), respectivamente. Constatou-se também que a presença da zeólita reduziu o grau de intumescimento desses materiais, devido ao decréscimo na elasticidade das cadeias poliméricas. Entretanto, nos resultados de dessorção observou-se que a presença da zeólita pode... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In order to apply agrochemicals in a controlled manner, and to reduce the damages to the health and environmental caused by these, two new hydrogels based on carboxymethylcellulose (CMC) and chitosan (Qs) polysaccharides supported on poly(methacrylic acid)-co-polyacrylamide (PMAA-co-PAAm) networks were synthesized. The influence of zeolite on the main properties of these materials such as sorption and desorption was also investigated. The stability of zeolite in the polymeric solution was studied by viscosimetry. These results showed that the addition of polysaccharide in the hydrogel-forming solution enables the obtaining of homogeneous nanocomposite hydrogels. The incorporation of zeolite into hydrogels was confirmed by the presence of spectroscopic bands at 798 cm-1 and 600 cm-1 in the FTIR nanocomposite spectra. Other indicatives were the reduction in pore volume and the presence of micropores in the pore walls of zeolite hydrogels, and increase in the residual mass of nanostructured hydrogels at 800ºC, observed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG), respectively. It was also observed that the presence of zeolite reduced the degree of swelling of these materials, due to the decrease in the elasticity of the polymeric chains. The results of desorption in saline medium show that the hydrogels studied in this work can reduce the presence of Al+3 ions, which in acidic soils are harmful to some crops. These results indicate that the hydrogel... (Complete abstract click electronic access below) / Doutor

Les objectifs principaux de ce travail étaient d'étudier la nature des composés de cuivre formés dans les nano-zéolithes en utilisant deux approches: (i) incorporation directe du Cu via une synthèse mono pot et (ii) incorporation post-synthèse du Cu suivi par une réduction chimique. Une étude détaillée de l'évolution des espèces de cuivre dans la suspension de nano-zéolithe LTL réduite avec de l'hydrazine a révélé la formation de nanoparticules de cuivre avec des dimensions limitées par la taille de canaux et des cages de la zéolithe. Cependant, avec un temps de réduction prolongé, les NPs de Cu ont tendance à migrer vers la surface de la zéolithe en raison de leur forte mobilité dans les milieux aqueux, et donne lieu à de grosses particules de cuivre, tout en conservant la structure de la zéolithe. La réduction du cuivre donne lieu à un système complexe contenant différentes espèces de cuivre: des résidus de Cu2+, Cu+ et des NPs de Cu. Les études par spectroscopie IRTF montrent l'hétérogénéité des cations Cu 2+ et Cu + dans la zéolithe Cu-LTL préparée par échange ionique. Il a été prouvé, que l'état et le comportement du cuivre dans la zéolithe LTL dépendent fortement de la méthode utilisée pour l'incorporation du Cu, soit par échange ionique, soit par incorporation directe du Cu. Il est devenu évident que le cuivre ajouté au mélange de synthèse possède un environnement distinct et occupe une position différente quand il est comparé à celui de l’échange ionique. Il est vraisemblablement partiellement localisé dans la charpente zéolithique ou /caché dans la structureet est inaccessible pour les molécules adsorbées. De plus, les modifications post-synthèse du matériau obtenu par synthèse directe entrainent un déplacement vers des positions hors structure d’un nombre important de Cu.De plus, les films minces de zéolithes contenant du métal avec des épaisseurs différentes ont été obtenue par un procédé de revêtement par centrifugation de supports de silicium et/ou des supports optiques CaF 2. Ce dernier a été utilisé pour la détection de CO en faible concentration à température ambiante et l’étude de la réponse optique ultrarapide du matériau photo-excité en résonance avec la bande du plasmon des NPs métalliques. En résume, ce travail couvre entièrement toutes les étapes de la synthèse, la modification, la caractérisation complète et l’utilisation de nano-cristaux de zéolithe contenant du métal. La combinaison des propriétés uniques des nanoparticules de cuivre et de la polyvalence des nano-zéolites donne lieu à des matériaux avancées intéressants pour de nombreuses d'applications dans des dispositifs de taille nanométrique, la détection sélective de produit chimique, la catalyse, etc. / The main objectives of this work were to study the nature of copper species formed in the nanosized zeolites using two approaches: (i) direct incorporation of Cu via one pot synthesis, and (ii) post synthesis incorporation of Cu followed by chemical reduction. A detailed study of the evolution of copper species in the LTL nanosized zeolite suspension reduced with hydrazine revealed the formation of copper nanoparticles with the dimensions limited by the size of zeolite channels and cages. However, with prolonged reduction time, the Cu NPs tend to migrate to the zeolite surface due to their high mobility in aqueous media, resulting in large copper particles, while the zeolite structure is preserved. The reduction of copper resulted in a complex system, containing different copper species: residuals of Cu2+, Cu+, CuNPs. The results of FTIR spectroscopy show the heterogeneity of Cu2+ and Cu+ cations in the Cu-LTL zeolite prepared by ion-exchange procedure. It has been proven, that the state and behavior of copper in LTL zeolite strongly depend on the method used for Cu inclusion: ion exchange or direct Cu incorporation. It became evident, that copper added to the synthesis mixture shows distinct environment and occupies different position when compared to ion exchange. It is presumably partially located in the zeolite framework or occluded in its walls and is inaccessible by adsorbed molecules. In addition, the post-synthesis modifications of the material obtained by direct synthesis cause the displacement of a significant amount of Cu to the extra-framework positions.Further, the metal containing zeolite thin films with different thickness were obtained by spin-coating approach on silicon wafers and CaF2 optical plates. The latter were after employed for detection of low concentration of CO at ambient temperature and investigation of the ultrafast optical response of the materials photo-excited in resonance with the plasmon band of the Me NPs. In summary, the present PhD thesis fully covers the all steps from the synthesis, modification, thorough characterization, and application of metal-containing nanosized zeolite crystals. The combination of unique properties of copper nanoparticles with versatility of nanozeolites give rise to the development of advanced materials which are interesting for many applications in nanoscale devices, selective chemical sensing, catalysis etc.

Theoretical investigation of microporous materials for adsorption and catalysis Microporous materials are defined by a presence of pores with diameter smaller than 2 nm. They comprise a large variety of materials from amorphous materials to very well defined crystalline materials like zeolites or metal organic frameworks. Microporous materials are industrially very important group of materials used for adsorption, gas capture, molecular sieving, or heterogeneous catalysis. Zeolites are by far the most important group of microporous materials due to their use as catalysts for the petroleum cracking. One of the main limitations of the zeolite use in catalysis is their limited pore size. This obstacle can be solved by use of hierarchical zeolites with a secondary mesopore network which allows overcoming the diffusion problems. The aims of this study can be divided into two parts. In the first part, the structures of two-dimensional and hierarchical zeolites were investigated theoretically to identify the structure of new materials and to obtain reliable models to study the hierarchical zeolites. In the second part, the catalytic properties of several microporous materials were modelled to explain their experimental activity. The results of this thesis were used to identify the structure of a large...

In dieser Arbeit werden die Ergebnisse mehrerer verschiedener Synthesemöglichkeiten für eine Optimierung der katalytischen Leistung durch Hierarchisierung zweier Molekularsiebe vorgestellt. Dabei wurde der ZSM-5 als Vertreter der Alumosilikate und der SAPO-34 (Silizium Aluminium-phosphat) ausgewählt, da diese als entsprechende MTH-Katalysatoren bereits wirtschaftliche Bedeutung erlangt haben. Die verschiedenen Möglichkeiten, ein solches hierarchisches Netzwerk zu generieren, werden dabei in Bezug auf die katalytische Leistung der jeweiligen Katalysatoren evaluiert und bewertet.

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.

Orientador: José Geraldo Nery / Resumo: A busca por novos materiais, principalmente materiais que apresentem múltiplas aplicações, continua atraindo pesquisas ao redor do mundo. Dentre os materiais pesquisados com esse intuito, os compósitos ganham destaque. Compósitos são materiais mistos formados pela união de dois ou mais materiais diferentes com a finalidade de produzir um material novo com propriedades distintas, em relação aos seus materiais de origem. Os compósitos podem ser aplicados em diferentes áreas, entre elas encontram-se a remediação ambiental e a hemostasia. A remediação ambiental se faz necessária principalmente pelo fato de que muitas fontes hídricas acabam sendo poluídas por resíduos nocivos a saúde humana e animal, como metais pesados, e o consumo destas águas acaba causando sérias doenças. Devido a isso a busca por agentes capazes de retirar estes poluentes da água torna-se necessária. Outro grande problema de saúde publica são as hemorragias incontroladas que continuam sendo umas das principais causas de mortes no mundo. Neste contexto, o objetivo deste trabalho foi sintetizar um compósito que apresente a capacidade de atuar tanto como agente de remediação ambiental como agente hemostático. O compósito foi sintetizado utilizando zeólita e quitosana como suas matrizes. O material foi caracterizado por Difração de Raios-X; Espectroscopia de Infravermelho e Microscopia Eletrônica de Varredura. O potencial de ação ambiental foi testado analisando a absorção de cátions de cádmio e chumbo, presentes... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The search for new materials, especially materials with multiple applications, continues to attract research from around the world. Among the materials researched for this purpose, composites stand out. Composites are mixed materials formed by joining two or more different materials in order to produce a new material with distinct properties relative to their source materials. Composites can be applied in different areas, including environmental remediation and hemostasis. Environmental remediation is necessary mainly due to the fact that many water sources end up being polluted by waste harmful to human and animal health, such as heavy metals, and the consumption of these waters ends up causing serious diseases. Because of this the search for agents capable of removing these pollutants from water becomes necessary. Another major public health problem is uncontrolled bleeding, which remains one of the leading causes of death worldwide. In this context, the objective of this work was to synthesize a composite that presents the ability to act as both environmental remediation agent and hemostatic agent. The composite was synthesized using zeolite and chitosan as their matrices. The material was characterized by X-ray diffraction; Infrared Spectroscopy and Scanning Electron Microscopy. The environmental action potential was tested by analyzing the absorption of cadmium and lead cations present in aqueous solution by the material, and the possible hemostatic application of the ma... (Complete abstract click electronic access below) / Mestre