There is an increasing demand for materials that are physically robust, easily recovered, and able to perform a wide variety of chemical functions. By combining hard and soft matter synergistically, organic-inorganic hybrid materials are potentially useful for a number of applications (e.g. catalysis, separations, sensing). In this respect, organic/ordered mesoporous silica (OMS) hybrids have attracted considerable attention, with an increasing emphasis on complex organic moieties achieved through multi-step reactions and polymerizations. It is on this front that we have focused our work, specifically in regard to polypeptides. Polypeptides are well suited organic components for hybrids as they provide a wide range of possible side chain chemistries (NH2, -SH, -COOH, -OH, etc.), chirality, and have conformations that are known to be responsive to external stimuli (pH, electrolytes, solvents, etc.). Our work has shown that N-carboxyanhydride chemistry offers a facile single step approach to the incorporation of dense polypeptide brushes in OMS. Modifying the initiator loading, pore size, pore topology, and monomer identity significantly impacted the properties of the obtained composites and peptide brush layers. Extending this work, a synthesis paradigm for preferentially grafting poly-L-lysine to the external and internal surfaces of SBA-15, a widely used OMS material, was developed. We observed that the pores of these hybrids could be opened and closed by the reversible swelling of the polypeptide layer. Similarly, novel bifunctional hybrids were synthesized by grafting polypeptides to the external surface of monodisperse OMS spheres that contain a thiol-functionalized core. The accessibility of the internal thiols to a fluorescent dye shows the potential of these hybrids for applications such as controlled uptake/release.

Over the past few decades there has been great interest in exploring alternatives to conventional separation methods due to their high cost and energy requirements. Membranes offer a potentially attractive alternative as they potentially address both of these points. The overarching theme of this dissertation is to design nanocomposite membranes for processes where existing separation schemes are inadequate. This dissertation focuses on three challenges: 1) designing organic-inorganic hybrid membranes for reverse-selective removal of alkanes from light gases, 2) defect-free inorganic nanocomposite membranes that have uniform pores, and 3) nanocomposite membranes for minimizing protein fouling in microfiltration applications. Reverse-selective gas separations that preferentially permeate larger/heavier molecular species based on their greater solubility have attracted considerable recent attention due to both economic and environmental concerns. In this study, dendrimer-ceramic hybrid membranes showed exceptionally high propane/nitrogen selectivities. This result was ascribed to the presence of stable residual solvent that affects the solubility of hydrocarbon species. Mesoporous silica-ceramic nanocomposite membranes have been fabricated to provide defectless mesoporous membranes. As mesoporous silica is iteratively synthesized in the ceramic macropores, the coating method and the surfactant removal step significantly affected permeance and selectivity. It was also shown that support layers can cause a lower selectivity than Knudsen limit. Membrane fouling which results from deposition and nonspecific adsorption of proteins on the membrane surface is irreversible in nature, and results in a significant decrease in the membrane performance. To address this problem, two approaches were explored: 1) control of the surface chemistry tethering alumina membranes with organic components and 2) development of a novel photocatalytic membrane that exhibits hydrophilicity and can be easily regenerated. Both approaches can offer a viable route to the synthesis of attractive membranes, in that 1) the density of protein-resistant organic groups such as PEG is controllable by changing scaffolds or synthesis conditions and 2) the photocatalytic nanocomposite membranes can open the way for a new regeneration method that is environmentally benign.

Nanoporous materials have attracted tremendous interest, investment and effort in research and development due to their potential applications in various areas such as membranes, catalysis, sensors, delivery, and micro devices. Controlling a nanoporous material’s microstructure is of great interest due to the strong influence on efficiency and performance. For particles, microstructure refers to particle size, shape, surface morphology, and composition. When discussing thin films, microstructure includes film thickness, crystal orientation and grain boundaries. In this respect, we focus to develop novel methods for the synthesis and characterization of nanoporous materials and their films, which are capable of controlling the microstructure of material. This dissertation is composed of two main sections and each explores the fabrication of a different nanoporous material: 1) A simple fabrication method for producing oriented MFI zeolite membranes with controlled thickness, orientation, and grain boundary; 2) A microfluidic synthesis of ordered mesoporous silica particles with controllable size, shape, surface morphology, and composition. The first section of this dissertation demonstrates a simple and commercially viable method termed the micro-tiles-and-mortar method to make continuous b-oriented MFI membranes with controlled membrane microstructure. This simple method allows for control of the thickness of the membrane by using plate-like seed crystals with different thicknesses along the b-axis (0.5 μm to 2.0 μm), as well as to manipulate the density and structure of grain boundaries. Microstructural effects of silicalite-1 membranes on the gas separation are investigated by measuring the permeation and separation for xylene isomers. In the second section of this dissertation, a new synthesis method for the ordered mesoporous silica particles with controllable microstructure is demonstrated. This novel method combines a microfluidic emulsification technique and nonaqueous inorganic synthesis with a diffusion-induced self-assembly (DISA). The systematic control of the particle microstructure such as size, shape, and surface morphology is shown by adjusting microfluidic conditions.

Template synthesis and mesostructural characterization of ordered mesoporous silica, titania and carbon materials have been systematically investigated in this study. In order to obtain a better understanding of the template-precursor relationship, there are two templates adopted in this research. One is the ¡§liquid crystal template (LCT)¡¨, composed of surfactants via self-assembly pathway; the other is the ¡§ordered silica spheres template¡¨, composed of monodispersed SiO2 spheres (~40 nm) via gravity sedimentation. This work was carried out in four related directions: (1) Synthesis and functionalization of ordered mesoporous silicate (MCM-41 and MCM-48) via cationic surfactant template; (2) Using anionic surfactant template-assisted via urea treatment to control the morphology of the TiO2; (3) Synthesis of ordered mesoporous anatase TiO2 via cationic surfactant template; (4) Synthesis of ordered mesoporous carbon from mesophase pitch solution via silica spheres template. Mesoporous silica materials MCM-41 and MCM-48 have been synthesized and identified. The MCM-41 has a hexagonal phase (p6m) with surface area of 1006.90 m2/g and pore size of 37.65 Å, The MCM-48 has cubic phase ( ) with surface area of 1093.34 m2/g and pore size of 29.20 Å. The calcined MCM-41was rehydrated by heating in water and functionalized with 3-amino propyltrimethoxysilane; this functionalized mesoporous silica is targeted as a template of metal oxides, such as TiO2. appears the same tendency of parent MCM-41 in the N2 sorption isotherm measurements. Nanocrystalline TiO2 rods and hollow-tubes with an engraved pattern on the surface have been prepared by the anionic template-assisted sol-gel synthesis via urea treatment and under hydrothermal condition. X-ray diffractometry (XRD) results indicate that these nanocrystallines consist predominantly of anatase TiO2, with minor amounts of rutile and brookite. The crystallographic facetting found from SEM and TEM further reveals the polymorphic nature of the nanocrystalline TiO2 thus prepared. A ¡§reverse micelle¡¨ formation mechanism taking into account the hydrothermal temperature, the pH effect of the sol-gel system, the isoelectric point, the formation of micelles, and the electrostatic interaction between the anionic surfactant and the growing TiO2 particulates is proposed to illustrate the competition between the physical micelle assembly of the ionic surfactants and the chemical hydrolysis and condensation reactions of the Ti precursors. Ordered mesoporous TiO2 materials with an anatase framework have been synthesized by using a cationic surfactant template and soluble peroxytitanates as Ti precursor through an S+I− self-assembly pathway. The low-angle X-ray diffraction (XRD) pattern of the as-prepared mesoporous TiO2 materials indicates a hexagonal mesostructure. XRD and TEM results and N2 sorption isotherms measurements indicate the calcined mesoporous TiO2 possesses an anatase crystalline framework having a maximum pore size of 6.9 nm and a maximum BET specific surface area of 284 m2/g. This ordered mesoporous TiO2 also demonstrates a high photocatalytic activity for degradation of methylene blue under ultraviolet irradiation. Under a lower carbonization temperature and with a mesophase pitch solution as the carbon precursor, ordered mesoporous carbon thick films with 35-nm pore size have been synthesized using SiO2 spheres as the template. The pore size of the mesoporous carbon thus fabricated was the smallest one ever reported using silica templates. SEM and TEM patterns show a discernible morphology of an ordered cubic close-packing of the mesopores interconnected via holes of 6 nm in diameter. From this study, the template synthesis has been proven to be an effective method to fabricate mesoporous silica, polymorphic titania, ordered mesoporous TiO2, and ordered mesoporous carbon materials. Further utilization of this template synthesis is expected to offer a variety of porous networks with a wide range of pore sizes, well-defined morphologies on controllable length scales, and various chemical functionalities to match the needs of different applications.

A contaminação de aguas pela mistura Benzeno, Tolueno, Etilbenzeno e Xilenos (BTEX) vem gerando a necessidade do desenvolvimento de metodologias altamente eficientes na remoção de poluentes e de metodologias analíticas para monitoramento ambiental suficientemente sensíveis, seletivos, reprodutíveis e rápidos. Nesse contexto, adsorventes com propriedades magnéticas aparecem como alternativas eficientes, de baixo custo e de fácil automação, inclusive possibilitando o desenvolvimento de metodologia analítica baseada na extração em fase sólida magnética (m-SPE), que vem ganhando interesse crescente por permitir extração rápida e análise efetiva dos poluentes com alta sensibilidade. A busca por adsorventes adequados exige o estudo de materiais com grande área superficial, funcionalizáveis e estáveis como as sílicas, mais especificamente uma comparação entre os tipos de sílica e do tipo de agente funcionalizante nas propriedades de adsorção/dessorção. Sílicas mesoporosas oraganofuncionalizas magnéticas com diferentes morfologias foram preparadas: sílica mesoporosa ordenada MCM-48 e MCM-41, bem como nanoparticulas esféricas de sílica mesoporosa (NPSiO2). A formação da silica mesoporosa ordenada começa com a preparação de um template de CTAB sobre o qual são depositados/formados os materiais MCM-41 e MCM-48. A concentração de CTAB deve ser controlada com cuidado pois estruturas com diferentes morfologias podem ser geradas variando-se esse parâmetro. As análises de espectroscopia FTIR, DRX e sorção de N2 revelaram que os materiais preparados são sílicas mesoporosas ordenadas com arranjo tipo giroide 3D (MCM-48) ou do tipo hexagonal (MCM-41) com área superficial respectivamente de 1212 m2.g-1 e 1159 m2.g-1. Além disso, as imagens de MET do material MCM-48 mostraram tamanho médio de partícula igual a 116 nm ± 15 nm. Para facilitar a remoção do adsorvente, nanopartículas de magnetita (SPION) foram incorporadas na superfície dos materiais adsorventes. O tempo de remoção típico foi determinado como sendo de 1 minuto. A organofuncionalização da sílica com octadecilssilano (C18), octilssilano (C8) e difenilssilano (Ph2) foi confirmada por espectroscopia FTIR e análise termogravimétrica demostrando a presença e a percentagem em massa dos grupos orgânicos em cada tipo de sílica mesoporosa. Usando como referência sílica gel 60 comercial (Sílica), foram comparadas as propriedades de adsorção frente a BTEX em agua, quando o agente funcionalizante é C8, C18 ou Ph2. Os resultados indicaram que as capacidades de adsorção, segundo o modelo de Langmuir, seguem a seguinte ordem C8≥C18>>Ph2. A partir disso, as propriedades de adsorção das demais sílicas funcionalizadas com C8 foram comparadas determinando-se que as capacidades de adsorção, segundo o modelo de Langmuir, estão na seguinte ordem: MCM-48>Sílica>NPSiO2>MCM-41. O nanocompósito organofuncionalizado MCM48-C8/SPION, que mostrou as melhores propriedades de adsorção, foi usado para a extração em fase sólida magnética (m-SPE) de BTEX em agua de posto de gasolina. Verificou-se que apenas 30 mg de adsorvente, 5 min de contato com a solução de BTEX, 1 min para remoção do adsorvente e 1 min para a extração foram suficientes para concentração/recuperação de BTEX de agua pela técnica de m-SPE, viabilizando a análise quantitativa, no caso por CG-MS. / The contamination of water bodies by Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) has prompted the development of more efficient methodologies for their removal and the development of sufficiently sensitive, selective, reproducible and fast analytical methods for environmental monitoring. In this context, adsorbent materials with magnetic properties appear as efficient, low cost and easy automation alternatives, including the development of analytical methods based on magnetic solid phase extraction (m-SPE), which has gaining increasing interest since allows rapid extraction and effective analysis of pollutants with high sensitivity. The search for suitable adsorbents requires the study of materials with large surface area, functionalizable and stable as the silica\'s family, more specifically a comparison between the types of silica and the type of functionalizing agent on their adsorption/desorption properties. Magnetic organofunctionalized mesoporous silicas with different morphologies were prepared: ordered mesoporous silica MCM-48 and MCM-41, as well as spherical nanoparticles of mesoporous silica (NPSiO2). The formation of ordered mesoporous silica begins with the preparation of a CTAB template on which silica is deposited/formed to produce MCM-41 and MCM-48 materials. The CTAB concentration must be carefully controlled since colloidal structures with different morphologies can be generated by varying this parameter. The FTIR, XRD and N2 sorption spectroscopy analyzes confirmed the preparation of ordered mesoporous silica materials with a gyroid 3D (MCM-48), or hexagonal type (MCM-41) arrangement respectively with a surface area of 1212 m2.g-1 and 1159 m2.g-1. In addition, the MET images of the MCM-48 material showed mean particle size equal to 116 nm ± 15 nm. To facilitate removal from water, magnetite nanoparticles (SPIONs) were incorporated into the surface of adsorbent materials. The typical removal time was determined to be 1 minute. The organofunctionalization of the silica with octadecylsilane (C18), octylsilane (C8) and diphenylsilane (Ph2) was confirmed by FTIR spectroscopy and thermogravimetric analysis demonstrating the presence and allowing the determination of the mass percentage of the organic fraction in each type of mesoporous silica. Using commercial silica gel (Silica) as reference, the adsorption properties toward BTEX in water were compared when the functionalizing agent is C8, C18 or Ph2. The results indicated that the adsorption capacities, according to the Langmuir model, decrease in the following order C8 ≥ C18 >> Ph2. From this, the adsorption properties of the C8 functionalized silicas were compared showing that the adsorption capacities according to the Langmuir model decrease in the following order: MCM-48 > Silica > NPSiO2 > MCM-41. The organofunctionalized nanocomposite MCM48-C8/SPION, exhibiting the best adsorption properties, was used in magnetic solid phase extraction (m-SPE) of BTEX from gas station water. Only 30 mg of adsorbent, 5 min of contact with the BTEX solution, 1 min to remove the adsorbent and 1 min for extraction were enough for concentration/recovery of BTEX in water by m-SPE technique suitable for quantitative analysis, in this case by CG-MS.

A contaminação de aguas pela mistura Benzeno, Tolueno, Etilbenzeno e Xilenos (BTEX) vem gerando a necessidade do desenvolvimento de metodologias altamente eficientes na remoção de poluentes e de metodologias analíticas para monitoramento ambiental suficientemente sensíveis, seletivos, reprodutíveis e rápidos. Nesse contexto, adsorventes com propriedades magnéticas aparecem como alternativas eficientes, de baixo custo e de fácil automação, inclusive possibilitando o desenvolvimento de metodologia analítica baseada na extração em fase sólida magnética (m-SPE), que vem ganhando interesse crescente por permitir extração rápida e análise efetiva dos poluentes com alta sensibilidade. A busca por adsorventes adequados exige o estudo de materiais com grande área superficial, funcionalizáveis e estáveis como as sílicas, mais especificamente uma comparação entre os tipos de sílica e do tipo de agente funcionalizante nas propriedades de adsorção/dessorção. Sílicas mesoporosas oraganofuncionalizas magnéticas com diferentes morfologias foram preparadas: sílica mesoporosa ordenada MCM-48 e MCM-41, bem como nanoparticulas esféricas de sílica mesoporosa (NPSiO2). A formação da silica mesoporosa ordenada começa com a preparação de um template de CTAB sobre o qual são depositados/formados os materiais MCM-41 e MCM-48. A concentração de CTAB deve ser controlada com cuidado pois estruturas com diferentes morfologias podem ser geradas variando-se esse parâmetro. As análises de espectroscopia FTIR, DRX e sorção de N2 revelaram que os materiais preparados são sílicas mesoporosas ordenadas com arranjo tipo giroide 3D (MCM-48) ou do tipo hexagonal (MCM-41) com área superficial respectivamente de 1212 m2.g-1 e 1159 m2.g-1. Além disso, as imagens de MET do material MCM-48 mostraram tamanho médio de partícula igual a 116 nm ± 15 nm. Para facilitar a remoção do adsorvente, nanopartículas de magnetita (SPION) foram incorporadas na superfície dos materiais adsorventes. O tempo de remoção típico foi determinado como sendo de 1 minuto. A organofuncionalização da sílica com octadecilssilano (C18), octilssilano (C8) e difenilssilano (Ph2) foi confirmada por espectroscopia FTIR e análise termogravimétrica demostrando a presença e a percentagem em massa dos grupos orgânicos em cada tipo de sílica mesoporosa. Usando como referência sílica gel 60 comercial (Sílica), foram comparadas as propriedades de adsorção frente a BTEX em agua, quando o agente funcionalizante é C8, C18 ou Ph2. Os resultados indicaram que as capacidades de adsorção, segundo o modelo de Langmuir, seguem a seguinte ordem C8≥C18>>Ph2. A partir disso, as propriedades de adsorção das demais sílicas funcionalizadas com C8 foram comparadas determinando-se que as capacidades de adsorção, segundo o modelo de Langmuir, estão na seguinte ordem: MCM-48>Sílica>NPSiO2>MCM-41. O nanocompósito organofuncionalizado MCM48-C8/SPION, que mostrou as melhores propriedades de adsorção, foi usado para a extração em fase sólida magnética (m-SPE) de BTEX em agua de posto de gasolina. Verificou-se que apenas 30 mg de adsorvente, 5 min de contato com a solução de BTEX, 1 min para remoção do adsorvente e 1 min para a extração foram suficientes para concentração/recuperação de BTEX de agua pela técnica de m-SPE, viabilizando a análise quantitativa, no caso por CG-MS. / The contamination of water bodies by Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) has prompted the development of more efficient methodologies for their removal and the development of sufficiently sensitive, selective, reproducible and fast analytical methods for environmental monitoring. In this context, adsorbent materials with magnetic properties appear as efficient, low cost and easy automation alternatives, including the development of analytical methods based on magnetic solid phase extraction (m-SPE), which has gaining increasing interest since allows rapid extraction and effective analysis of pollutants with high sensitivity. The search for suitable adsorbents requires the study of materials with large surface area, functionalizable and stable as the silica\'s family, more specifically a comparison between the types of silica and the type of functionalizing agent on their adsorption/desorption properties. Magnetic organofunctionalized mesoporous silicas with different morphologies were prepared: ordered mesoporous silica MCM-48 and MCM-41, as well as spherical nanoparticles of mesoporous silica (NPSiO2). The formation of ordered mesoporous silica begins with the preparation of a CTAB template on which silica is deposited/formed to produce MCM-41 and MCM-48 materials. The CTAB concentration must be carefully controlled since colloidal structures with different morphologies can be generated by varying this parameter. The FTIR, XRD and N2 sorption spectroscopy analyzes confirmed the preparation of ordered mesoporous silica materials with a gyroid 3D (MCM-48), or hexagonal type (MCM-41) arrangement respectively with a surface area of 1212 m2.g-1 and 1159 m2.g-1. In addition, the MET images of the MCM-48 material showed mean particle size equal to 116 nm ± 15 nm. To facilitate removal from water, magnetite nanoparticles (SPIONs) were incorporated into the surface of adsorbent materials. The typical removal time was determined to be 1 minute. The organofunctionalization of the silica with octadecylsilane (C18), octylsilane (C8) and diphenylsilane (Ph2) was confirmed by FTIR spectroscopy and thermogravimetric analysis demonstrating the presence and allowing the determination of the mass percentage of the organic fraction in each type of mesoporous silica. Using commercial silica gel (Silica) as reference, the adsorption properties toward BTEX in water were compared when the functionalizing agent is C8, C18 or Ph2. The results indicated that the adsorption capacities, according to the Langmuir model, decrease in the following order C8 ≥ C18 >> Ph2. From this, the adsorption properties of the C8 functionalized silicas were compared showing that the adsorption capacities according to the Langmuir model decrease in the following order: MCM-48 > Silica > NPSiO2 > MCM-41. The organofunctionalized nanocomposite MCM48-C8/SPION, exhibiting the best adsorption properties, was used in magnetic solid phase extraction (m-SPE) of BTEX from gas station water. Only 30 mg of adsorbent, 5 min of contact with the BTEX solution, 1 min to remove the adsorbent and 1 min for extraction were enough for concentration/recovery of BTEX in water by m-SPE technique suitable for quantitative analysis, in this case by CG-MS.

Les phosphures de métaux de transition nanométriques trouvent de nombreuses applications, notamment en catalyse hétérogène. Les silices mésoporeuses organisées (SMO) de type SBA-15, grâce à leurs paramètres physico-chimiques ajustables (surface spécifique, taille de pores, épaisseur de parois, etc.) et la reproductibilité de leurs synthèses, sont des supports de nanoparticules (NPs) de choix. Dans ce contexte, l'objectif de cette thèse est de synthétiser des NPs de phosphure de cobalt dans les pores de matrices de type SBA-15 à partir de clusters organométalliques comme uniques précurseurs. Dans une première partie, nous étudions le comportement de trois clusters contenant un ou plusieurs ligands phosphorés à haute température. Ceux-ci présentent des rapports Co/P différents, ce qui a un impact direct sur la phase phosphure obtenue après activation. Nous suivons également l'influence de l'atmosphère et de la température sur les phases formées lors du traitement thermique. Pour contrôler la taille et la polydispersité des NPs étudiées, nous avons imprégné le cluster précurseur [Co4(CO)10(µ-NH(PPh2)2)] dans des SMO de type SBA-15. L'atmosphère et la température choisies pour le traitement thermique influent sur la phase obtenue, comme précédemment, mais les conditions ne sont pas identiques. De plus, des phases parasites ferromagnétiques sont formées et des lavages à l'acide chlorhydrique concentré sont nécessaires pour s'en affranchir. Enfin, la préparation de grandes quantités de produit (transfert d'échelle) requiert l'utilisation d'un volume contrôlé lors du traitement thermique, pour assurer une homogénéité dans l'échantillon. / Nanosized transition metal phosphides find applications in various fields, including heterogeneous catalysis. Ordered mesoporous silica (OMS) such as SBA-15 are supports of choice for nanoparticles (NPs), since they feature adjustable microstructural parameters (specific surface area, pore size, wall thickness, etc.) and reproducible synthesis conditions. In this context, the goal of this PhD work is to synthesize cobalt phosphide NPs within the pores of SBA-15-type OMS, starting from organometallic clusters as single-source precursors. First, we study the behavior of three organometallic clusters bearing one or more phosphine-based ligands at high temperatures. Depending on the initial Co/P ratio, those clusters afford different phosphide phases. We also monitored the influence of the atmosphere and the temperature during the thermal treatment on the phases obtained. To control size and polydispersity of the NPs, we impregnated the cluster precursor [Co4(CO)10(µ-NH(PPh2)2)] in SBA-15-type OMS. As in the previous case, atmosphere and temperature influence the obtained phase, but the conditions are different. Moreover, ferromagnetic impurities are formed and it is necessary to wash the samples with concentrated hydrochloric acid to remove them. Finally, larger quantities of product can be prepared (scale-up) but the volume of sample thermally treated at once needs to be controlled precisely to ensure homogeneity of the final product.

Developing effective methods of generating thin metal oxide films are important for sensing and separations applications. An obstacle to device fabrication is controlling the size and spatial orientation of domain level pores while retaining the ability to generate arbitrary device level patterns. Well-ordered hexagonally packed cylindrical pores were created by taking advantage of block copolymer self-assembly followed by selective condensation of silica precursors using supercritical carbon dioxide as the solvent. It was possible to control the pore size by choosing PEO-PPO-PEO (Pluronic® series) triblock copolymers of differing molecular weights. These processes were then incorporated with conventional lithographic techniques to generate patterns on the device scale. The first route involves replacement of the organic acid catalyst with a photoacid generator that restricts acid formation by masking pre-determined regions then exposing to UV light. The second route is similar except that addition of a cross-linking agent limits acid diffusion while reversing the tone of the final pattern. The third route avoids acid diffusion altogether and generates the pattern through reactive ion etching through a sacrificial photoresist. A completely different fourth route was taken and nanoimprint lithography was used to generate sub-micron patterns with alternate block copolymers. The feasibility of the preliminary devices generated in this thesis has been examined through particle diffusion experiments. Samples were soaked in a fluorescent dye then exposed to multiple sizes of gold nanoparticles. Fluorescence quenching was then monitored to determine pore accessibility.

No description available.

Ce travail est consacré à la préparation de matériaux mésoporeux à partir de cristaux liquides formés avec des tensioactifs fluorés selon le mécanisme transcriptif LCT. Les paramètres de synthèse ont été optimisés pour la préparation de silices mésostructurées à partir de la phase hexagonale du système eau/C8F17C2H4(OCH2CH2)9OH. Les résultats montrent une corrélation entre le diamètre des pores des matériaux et les diamètres hydrophobes mesurés dans les cristaux liquides. L'incorporation de TiO2 dans une matrice silicatée selon la méthode de coprécipitation a été réalisée en utilisant soit des micelles (mécanisme d'auto-assemblage coopératif CTM), soit la phase hexagonale du système C8F17C2H4(OCH2CH2)9OH/eau (mécanisme transcriptif LCT). Dans les deux cas, l'incorporation de titane conduit à une perte de la structure et à une diminution de la surface spécifique. L'utilisation du mécanisme CTM favorise la formation de TiO2 anatase en surface du matériau, tandis que pour le mécanisme LCT, la substitution du silicium par le titane au coeur du matériau a été mise en évidence. Des films minces mésostructurés à base de TiO2 ont été réalisés à partir de la méthode EISA. Les analyses par diffraction des rayons X à incidence rasante couplées à des mesures de réflectivité ont permis de mettre en évidence la structure des films et de déterminer les épaisseurs des couches qui constituent les films. Enfin, une méthode originale de synthèse de matériaux mésoporeux organisés à base de TiO2 a été développée. La précipitation de TiO2 dans la mésophase hybride est déclenchée à l'aide d'un traitement par NH3 (g). La structure des matériaux est conservée après l'étape de calcination laquelle permet de cristalliser TiO2 en phase anatase. L'activité photocatalytique de ces matériaux a ensuite été testée sur la réaction de photodégradation du méthylorange / This work deals with the preparation of mesoporous materials from fluorinated liquid crystals via the LCT mechanism. Synthesis parameters have been optimized for the preparation of ordered mesoporous silica with the hexagonal H1 phase of water/C8F17C2H4(OCH2CH2)9OH system. Results show a correlation between pore diameters of materials and hydrophobic diameters measured in liquid crystals. According to the coprecipitation method, incorporation of TiO2 in a silica matrix, synthesized using micelles (via the cooperative templating mechanism CTM) or the hexagonal phase of C8F17C2H4(OCH2CH2)9OH/water system (via liquid crystal templating mechanism LCT). Both pathways lead to a loss of mesopore ordering and a decrease of the specific surface area when titania content increases. If materials are prepared via CTM mechanism TiO2 is present on the surface whereas TiO2 is in the bulk when LCT mechanism is used. Mesoporous thin films have been prepared via EISA method. Grazing incidence small angle X-Ray scattering and reflectivity analysis have been used to define the structure of films and the thickness of the different layers. Finally an original method has been developed for the preparation of ordered titania mesoporous materials. Precipitation of titania in the hybrid mesophase is activated by a NH3 treatment. The structure is preserved after calcination step which allow the formation of TiO2 anatase. Photocatalytic activity of these materials has been tested on the photodegradation of methylorange