Le but de ce projet de thèse a été d’établir une nouvelle méthodologie permettant d’immobiliser des espèces paramagnétiques sur des silices mésoporeuses afin d’optimiser le processus de polarisation dynamique nucléaire. Pour ce faire, différentes matrices polarisantes, nommées HYPSO pour « HYbrid Polarizing SOlids », ont été préparées par un procédé sol-gel. Ces solides sont hautement poreux et des espèces paramagnétiques y sont liées de manière covalente. Un des avantages notable de cette méthode consiste à s’affranchir « d’agent glaçant » en raison d’une répartition homogène et aléatoire des radicaux à la surface des matériaux. Deux types de matrices polarisantes, HYPSO 2 et HYPSO 3 ont révélé des polarisations distinctes : P(1H)= 50% et P(1H)= 63%. Cette différence a été expliquée par l’influence de la matrice de silice qui offre de meilleures performances lorsque sa porosité est interconnectée dans les 3 dimensions de l’espace. Suite à ces résultats, de nouveaux matériaux (HYPSO 5) ont été préparés. L’influence de la taille des pores ainsi que celle des grains de silice sur la polarisation ont été étudiées. Des performances remarquables : P(1H)= 99% (± 5%) et P(13C)= 51 % ont été enregistrées, témoignant ainsi de l’efficacité de cette nouvelle méthode. De plus, les premières images IRM utilisant les HYPSO 5 en tant que matrices polarisantes ont été obtenues après hyperpolarisation d’une solution d’acétate de sodium de référence. Enfin, nous nous sommes intéressés à une nouvelle formulation basée sur des xérogels de silice. Des résultats préliminaires ont montré de bonnes polarisations avec la capacité d’utiliser un même monolithe pour polariser différents liquides / The goal of this PhD project was to develop a new methodology allowing to immobilize paramagnetic species on mesoporous silica in order to optimize the dynamic nuclear polarization process. For this purpose, different polarizing matrices, denoted as HYPSO for “HYbrid Polarizing SOlids”, were prepared through a sol-gel process. These solids are highly porous and paramagnetic species are covalently attached onto the surface. One of the noticeable benefit of this method lies in the possibility to remove the “glass forming agent” because of a homogeneous and random repartition of the radicals onto the surface of these materials. Two types of polarizing matrices, HYPSO 2 and HYPSO 3 gave distinct polarizations: P(1H)= 50% and P(1H)= 63%. This difference was explained by the influence of the silica matrix which provides better performances when its porosity is interconnected in the 3 dimensions of the space. Following these results, new materials (HYPSO 5) were prepared. The influence of the pore sizes as well as those of the silica grains on the polarization were studied. Remarkable performances: P(1H)= 99% (± 5%) et P(13C)= 51 % were recorded, thereby demonstrating the efficiency of this new method. Moreover, the first MRI pictures using HYPSO 5 as polarizing matrices were obtained after hyperpolarization of a sodium acetate solution. Finally, we were interested to a new formulation based on silica xerogels. Preliminaries results showed good polarizations and the ability to use only one monolith to polarize different liquids

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-02-27T21:17:17Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Ariane Caroline.pdf: 6051822 bytes, checksum: c1a56154adb0e6b52f2cba5bb3654d0b (MD5) / Made available in DSpace on 2019-02-27T21:17:17Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Ariane Caroline.pdf: 6051822 bytes, checksum: c1a56154adb0e6b52f2cba5bb3654d0b (MD5) Previous issue date: 2018-12-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho reporta a preparação, caracterização e aplicação de novos materiais híbridos silsesquioxanos, obtidos a partir do método sol-gel de síntese, que consistiu em reações de hidrólise e policondensação dos precursores a base de sílica e por meio da reação SN2 dos precursores com os ligantes orgânicos 4-(aminometil)piridina e imidazol, obtendo assim o Si4ampy+Cl- e o SiImi+Cl-, respectivamente. Os silsesquioxanos nitrogenados foram submetidos a técnicas de caracterização como RMN, DRX, MEV, UV-VIS, FTIR e BET para confirmação das estruturas apresentadas nesta tese, bem como a organofuncionalização dos materiais. No caso do Si4ampy+Cl-, verificou-se dois sítios de reação com ligação do carbono –α do grupo npropil ao nitrogênio do grupamento amino e do nitrogênio do anel piridínio, com proposta de dois arranjos da cadeia carbônica. O Si4ampy+Cl- foi aplicado na construção de eletrodos modificados com a NiTsPc, utilizando a técnica LbL para a fabricação de filmes finos. O eletrodo na configuração (Si4ampy+Cl-/NiTsPc)11 foi aplicado como sensor eletroquímico sensível ao nitrito, com r = 0,999 na faixa de 0,113 mmol L-1 a 0,860 mmol L-1, LD e LQ de 0,026 mmol L-1 e 0,127 mmol L-1, respectivamente e os valores de desvio-padrão foram de aproximadamente 3%, estando de acordo com recomendações da ANVISA e Inmetro. Outro emprego do Si4ampy+Cl- foi na estabilização de nanopartículas de prata para fabricação de filmes finos. A presença das Ag-NPs/Si4ampy+Cl- foi confirmada por UV-VIS, pela banda plasmon em 426 nm, as quais apresentaram distribuição com tamanho aproximado entre 12 e 131 nm, constatado por DLS e corroborado por MEV, apresentando boa estabilidade (= +43,4 mV). As Ag-NPs/Si4ampy+Cl- mostraram-se promissoras na modificação do eletrodo ITO com a NiTsPc, apresentando um crescimento linear do filme LbL e processos redox referentes à oxirredução do centro metálico e à oxidação do anel da ftalocianina vistos por voltametria cíclica, exibindo a capacidade do eletrodo modificado (Ag-NPs/Si4ampy+Cl-/NiTsPc)7 em eletrocatalisar espécies químicas. No geral, os eletrodos modificados (Si4ampy+Cl-/NiTsPc)11 e (Ag-NPs/Si4ampy+Cl-/NiTsPc)7 proporcionaram aprimoramento na resposta de corrente anódica e redução do potencial de oxidação comparado com o eletrodo não-modificado (ITO) em presença de nitrito. O SiImi+Cl- que foi destinado a adsorção dos íons Cu2+, Cd2+ e Ni2+, apresentou capacidade de troca iônica de 2,944 mmol g-1, resultado considerado excelente de acordo com a literatura para a aplicação proposta. Os resultados de adsorção mostraram a viabilidade do uso do SiImi+Cl- como eficiente material adsorvente, exibindo maior afinidade para os íons Cu2+ em pH 4. Ao aplicar os modelos de Langmuir e Freundlich nas isotermas de adsorção, verificou-se que tanto o pH como a natureza do íon são fatores que influenciaram o ajuste das isotermas aos modelos propostos. / This work reports the preparation, characterization and application of new silsesquioxanes hybrid materials obtained from the sol-gel synthesis method, which consisted of hydrolysis and polycondensation reactions of the silica-based precursors and SN2 reaction of the precursors with 4-(aminomethyl)pyridine and imidazole groups, obtaining Si4ampy+Cl- and SiImi+Cl-, respectively. Silsesquioxanes with nitrogen groups were characterized by techniques such as NMR, XRD, MEV, UV-VIS, FTIR and BET to confirm the structures presented in this thesis, as well as the materials functionalization. In the case of Si4ampy+Cl- two reaction sites were observed with carbon-α of the n-propyl group bonding with the amino group and the pyridinium ring, having as proposal two arrangements of the carbonic chain. The Si4ampy+Cl- was applied in the construction of electrodes modified with NiTsPc using the LbL technique for the thin films manufacture. The electrode in the configuration (Si4ampy+Cl-/NiTsPc)11 was applied for nitrite electrochemical sensor, with r = 0.999 in the range of 0.113 mmol L-1 to 0.860 mmol L-1, LD and LQ of 0.026 mmol L-1 and 0.127 mmol L-1, respectively and standard deviation values of approximately 3%, according to recommendations of ANVISA and Inmetro. Another use of Si4ampy+Cl- was the stabilization of silver nanoparticles for the thin films production. The presence of Ag-NPs/Si4ampy+Cl- was confirmed by UV-VIS technique by the plasmon band at 426 nm which presented a distribution with approximate size between 12 and 131 nm, verified by DLS and MEV, presenting good stability (= +43.4 mV). The Ag-NPs/Si4ampy+Cl- showed promising in the modification of the ITO electrode with NiTsPc, showing linear growth of the LbL film and redox processes related to the oxidation of the metal center and to the oxidation of the phthalocyanine ring observed by cyclic voltammetry, exhibiting the performance of the modified electrode (Ag-NPs/Si4ampy+Cl-/NiTsPc)7 to electrocatalyse chemical species. In general, the modified electrodes (Si4ampy+Cl-/NiTsPc)11 and (Ag-NPs/Si4ampy+Cl-/NiTsPc)7 obtained an improvement in the anodic current response and reduction of the oxidation potential compared to the unmodified electrode (ITO) in the presence of nitrite. The SiImi+Cl- was used to adsorb Cu2+, Cd2+ and Ni2+ ions and presented ion exchange capacity of 2.944 mmol g-1, which was considered excellent according to the literature for the proposed application. The adsorption results showed the viability of using SiImi+Cl- as an efficient adsorbent material, exhibiting a higher affinity for the Cu2+ ions at pH 4. Applying the Langmuir and Freundlich models to the adsorption isotherms, it was verified that both the pH as the nature of the ion are factors that influenced the adjustment of the isotherms to the proposed models.

Depuis une décennie, dans le domaine de la nanomédecine, les recherches s’orientent de plus en plus vers l’élaboration de nanomatériaux multifonctionnels avec l’espoir d’améliorer la précision des diagnostics ou encore l’efficacité des traitements à mettre en place. Dans ce contexte, notre travail visait à mettre en œuvre des nanoparticules hybrides Au@SiO2 de type cœur-coquille associant les propriétés photothermiques de la phase métallique à la fonction délivrance de médicaments du réseau inorganique poreux. Avec le greffage d’obturateurs organiques à l’entrée des pores de la silice, ces assemblages deviennent dès lors de véritables nanosystèmes « mécanisés ». La première partie du travail a donc concerné la synthèse du cœur du nanomatériau (nanoparticules d’or creuses appelées « nanoshells ») réalisée par un procédé de remplacement galvanique. L’influence des paramètres de synthèse sur la morphologie et la structure, sur l’état de surface ainsi que sur les propriétés optiques des nanoparticules a été largement discutée ici. Après la coupe transverse des nanoshells ainsi élaborées, les techniques d’analyse de surface (XPS, AES) ont permis de préciser la formation d’un alliage Ag-Au de composition hétérogène. L’élaboration d’une coquille de silice mésoporeuse autour des cœurs métalliques a ensuite été réalisée. Après avoir démontré le potentiel de ces nanoparticules pour le confinement moléculaire, les nano-objets Au@SiO2 ont finalement été fonctionnalisés par des assemblages supramoléculaires constitués d’un diaminoalcoxysilane (greffé à la surface) en interaction avec un macrocycle. Le couplage spécifique des techniques XPS et RMN a permis de caractériser précisément la fonctionnalisation. Une ouverture à ce travail a été initiée vers des systèmes davantage biocompatibles avec l’élaboration cette fois-ci d’une coquille hybride polymère/silice. Une première série de tests in vitro a permis d’explorer l’impact et l’interaction des nanoparticules avec des cellules de type HaCaT et a montré tout le potentiel de la poly-L-lysine dans cette approche. Cette étude originale propose de nouvelles informations dans l’étude des systèmes nanostructurés avec une caractérisation physico-chimique appropriée qui signale l’importance des phénomènes aux interfaces au sein de l’architecture hybride. Les perspectives visent maintenant à une optimisation fonctionnelle de ces nano-objets pour des applications en nanomédecine. / Nowadays, in the field of nanomedecine, the major challenge is to design multifunctional nanomaterials in order to improve diagnosis and treatment efficiency. In this context, our work has concerned the conception of hybrid Au@SiO2 core-shell nanoparticles combining the photothermal properties of the gold core and the drug delivery function associated with the inorganic porous network. The entrance pore functionalization with gatekeepers leads finally to mecanized nanosystems. The first part of the work has concerned the core material synthesis (hollow gold nanoparticles called « nanoshells ») which has been achieved by a galvanic replacement reaction. The influence of synthesis parameters on the structure, the morphology and on the optical properties has been studied. Moreover, the analysis of a nanoparticle cross-section by XPS and AES has evidenced the formation of a heterogeneous Ag-Au alloy. Then, the growth of a mesoporous silica shell on the metal cores has been conducted leading to Au@SiO2 nanomaterials. After demonstrating the potential of these core-shell nanoparticles for hosting molecules, the nano-objects have been functionalized with supramolecular nanovalves based on a diaminoalkoxysilane (grafted on the silica surface) interacting with a macrocycle. The combination of XPS and NMR allowed us to characterize precisely the functionalization. In a last section, we have been interested in the design of biocompatible systems with the elaboration of a hybrid polymer/silica shell. The in vitro effect and interaction of nanoparticles with HaCaT cells have been studied; the first results have demonstrated a real interest for using poly-L-lysine in these systems. This original study offers new details about the physico-chemical characterization of nanostructured systems which highlights the important role of interfaces in hybrid materials. The perspectives will concern the optimization of the synthesized nanosystems for direct nanomedicine applications.

Submitted by (lucia.rodrigues@ufrpe.br) on 2017-02-13T12:58:51Z No. of bitstreams: 1 Aline de Andrade Alves.pdf: 1102339 bytes, checksum: b203a6432ccdaef9ba8b28ee763a99f6 (MD5) / Made available in DSpace on 2017-02-13T12:58:51Z (GMT). No. of bitstreams: 1 Aline de Andrade Alves.pdf: 1102339 bytes, checksum: b203a6432ccdaef9ba8b28ee763a99f6 (MD5) Previous issue date: 2012-02-27 / The organofunctionalized silica was used as the solid support in the study of photophysical properties of lanthanides, in particular the Eu (III) ions, which functions as structural probe has been thoroughly discussed seeking new technological applications. In this study, were synthesized two novel organofunctionalized silica matrices and new lanthanide complexes containing sialic acid as ligand. These compounds were characterized via luminescence spectroscopy, infrared spectroscopy, thermal analysis and elemental analysis. Two routes were used to obtain functionalized silica with thenoyltrifluoracetonate. The elemental analysis and infrared spectroscopy data suggest the minimum structures proposed. The europium complex with sialic acid showed weak luminescence, which was expected due to even have low molar extinction coefficient. The solid phase synthesized consisting of silica coordinated to europium complex with thenoyltrifluoracetonate was sensitive to sialic acid. / A utilização da sílica organofuncionalizada como suporte sólido no estudo das propriedades fotofísicas dos íons lantanídeos em especial o íon Eu (III) que funciona como sonda estrutural, tem sido bastante discutido visando novas aplicações tecnológicas. Neste trabalho, foram sintetizadas duas matrizes inéditas de sílica organofuncionalizadas e novos complexos de lantanídeo contendo como ligante o ácido siálico. Esses compostos foram caracterizados via espectroscopia eletrônica de luminescência, espectroscopia na região do infravermelho, análise térmica e análise elementar. Foram utilizadas duas Rotas para obtenção da sílica funcionalizada com tenoiltrifluoroacetonato. Os dados de análise elementar e espectroscopia na região de infravermelho sugerem as estruturas mínimas propostas. Os complexos de európio com o ácido siálico apresentaram fraca intensidade de luminescência, o que já era esperado devido ao mesmo ter baixo coeficiente de extinção molar. A fase sólida sintetizada, constituída por sílica funcionalizada e coordenada a um complexo de tenoiltrifluoracetonato e európio é sensível ao ácido siálico.

Le sujet de la thèse porte sur l'élaboration de nouveaux matériaux MOx (M=Ti,Zr) nanostructurés et fonctionnalisés en surface pour l'élimination des micro-polluants HAP dans des effluents aqueux. Compte tenu de la nature des polluants visés, nous avons choisi de travailler sur des fragments organiques (R) mono- ou poly-aromatiques, pouvant former des complexes de transfert de charge (π-stacking) avec les HAPs en solution, étant donné que ces interactions sont effectives en milieu aqueux. Dans le but d'obtenir un greffage efficace et pérenne, nous avons sélectionné des greffons phosphonates R-P(O)(OH)2 plutôt que carboxylates R-COOH. Ce projet a donc consisté en l'élaboration de différents ligands de type acides phosphoniques comportant au moins une insaturation via une addition d'Aza-Michael. La modification de précurseurs hétéroleptiques a pu conduire à la formation de matériaux hybrides en une seule étape par le procédé sol-gel. Cette approche moléculaire « bottom-up & one pot » a permis l'obtention de nanoparticules cristallisées (pour le titane) et fonctionnalisées en surface de façon contrôlée. Ces nanomatériaux ont ensuite été évalués, seuls ou supportés sur textiles, pour l'élimination de 16 HAP (considérés prioritaires par l'agence américaine EPA). Les matériaux nanocomposites (textiles / oxyde) fonctionnalisés ont démontré les mêmes performances d'adsorption des HAPs que les poudres hybrides nano-structurés, tout en apportant l'avantage supplémentaire de traiter efficacement de plus grands volumes d'eaux pollués en un temps plus court. Enfin ces matériaux peuvent être recyclés ce qui est totalement impossible avec les matériaux carbonés usuels du type charbon actif / The subject of the thesis concerns the elaboration of new hybrid nanomaterials Mox (M=Ti, Zr)n for the elimination of PAH micro-pollutants in aqueous effluents. Taking into account the nature of such pollutants, we chose to work on organic fragments (R) mono- or poly-aromatic, which could form complexes or transfer (p-stacking) with the HAPs in solution, given that these interactions are effective in aqueous media. In order to obtain an effective and long-lasting grafting, we selected phosphonates R-P (O)(OH)2 ligands rather than carboxylates ones R-COOH. This poject thus consisted of the elaboration of different ligands of phosphonic acid containing at least one insaturation via an Aza-Michael addition. Heteroleptic molecular precursors were obtained by reaction between metallic alkoxides and various phosphonic acids, and led us hybrid nanomaterials in a single stage by sol-gel process. This molecular approach “bottom-up & one pot” allowed the obtaining of crystallized nanoparticles (for the titanium) and the control of the surface functionalization. The performances of these nanomaterialsThe performances of these nanomaterials were then tested, alone or supported on fabrics, for the elimination of HAP (considered as priority by the American agency EPA). The results of adsorption of the HAPs on the various synthesized nanomaterials show an exceptional efficiency of materials to adsorb 16 HAPs. The nanocomposite materials (textile/oxides) demonstrated the same performances of adsorption of the HAPs as the hybrid nano-structured powders, while bringing the additional benefit to treat effectively bigger volumes of waters polluted within shorter time. Finally these materials can be recycled which is totally impossible with the usual carbon materials such as activated charcoal

Depuis plusieurs dizaines d'années, les matériaux hybrides organiques-inorganiques constituent une classe de matériaux particulièrement bien adaptée aux applications en optique intégrée. Le réseau minéral, élaboré par procédé sol-gel, confère au matériau la tenue mécanique. Quant au réseau organique, qui est réticulable par voie photochimique, il permet la formation des systèmes guidants. Des travaux antérieurs réalisés au sein de notre laboratoire ont montré le potentiel d'un matériau à base d'un précurseur hybride 2-(3,4 epoxycyclohexylethyltrimethoxysilane) (EETMOS) pour l'application en optique intégrée. Bien que la qualité des composants réalisés à 1,31µm se soit révélée satisfaisante, un problème subsiste : une trop forte atténuation à 1,55 µm. La transmission optique autour de ces longueurs d'ondes est limitée par la présence des groupements OH et CH aliphatiques.L'objectif principal de ce travail est de développer une nouvelle génération de matériaux hybrides avec une très grande réactivité et de diminuer la quantité de groupements impliqués dans l'atténuation. Nous avons choisi la fonction vinyl éther comme fonction organique grâce à sa grande réactivité par voie cationique en comparaison avec la fonction époxyde. Nous avons étudié la double fonctionnalité de polymérisation du nouveau matériau hybride à base d'un vinyl éther silane. En premier lieu, les réactions d'hydrolyse et de polycondensation du sol ont été suivies par la spectroscopie RMN liquide du Si-29 en fonction du temps, de la température et du pH de l'eau impliquée dans l'hydrolyse. Le but était d'obtenir le plus haut taux d'oligomère multifonctionnel possible et le minium de groupement OH. La photopolymérisation de type cationique de la fonction vinyl éther a ensuite été étudiée, en utilisant la spectroscopie d'absorption dans l'infrarouge moyen. En présence du photoamorceur diaryliodonium, la photopolymérisation a été étudiée en suivant l'évolution de la bande d'absorption de la double liaison vinyl éther avant et après irradiation. La photopolymérisation cationique est rapidement initiée dès le début de l'exposition aux UV, ce qui prouve la réactivité important de la fonction vinyl éther. En utilisant la spectroscopie d'absorption dans le proche infrarouge, les résultats montrent des niveaux d'atténuation très prometteurs pour l'utilisation de ce matériau en optique intégré à 1,31 et 1,55 µm. / In the last few years, organic-inorganic hybrid materials were particularly attractive for integrated optical circuits. Hybrid network could be prepared by the formation of inorganic and organic network simultaneously through sol-gel technique and photopolymerization process.A composition based on [2-(3, 4 epoxycyclohexylethyltrimethoxysilane)] has already allowed the fabrication of optical integrated devices. The organic polymerization is on a cationic way. Results show the contributions of OH and aliphatic CH groups to the attenuation in the third telecommunication window located at 1,55 µm.The main objective of this work is to remove this difficulty by developing a new generation of hybrid materials with a very high reactivity and low amount of groups involved in the attenuation. We have chosen vinyl ether function as an organic part because of their well known high polymerization rates via cationic way which are faster than the epoxide function and which lead to no OH groups generation and a very low aliphatic CH groups introduction.In this work, we study the dual functional structure of a new vinyl ether alkoxysilane hybrid precursor. Firstly, hydrolysis and polycondensation of vinyl ether based solution are followed by liquid and solid Si-NMR spectroscopy. The kinetic reaction is followed as a function of time, temperature and pH of the water involved in the hydrolysis, in order to obtain the highest reactive multifunctional oligomer and the lowest OH groups. Secondly, results of the cationic photopolymerization of vinyl ether- based monomers are also reported, using middle infrared spectroscopy. In the presence of diaryliodonium photoinitator, the photopolymerization is studied by monitoring the absorption band of vinyl ether double bond before and after irradiation. The cationic photopolymerization occurs rapidly upon UV-exposure and vinyl ether monomers proved to be very effective monomers. Using near infrared spectroscopy, results show promising attenuation for the use of this material in integrated optic at 1,31 µmand 1,55 µm.

Ce travail rapporte l'élaboration par voies humides (sol-gel, précipitation) et sèche (mécanosynthèse) de photocatalyseurs originaux à l’état de poudre pure ou supportées sur des fibres de palygorskite (Pal), composant d’une argile brute naturelle d’origine marocaine. TiO2 seul, non dopé ou dopé au soufre, et couplé avec CuO fut utilisé comme composant actif principal. Ag2CO3 fut également étudié comme composant alternatif en raison de sa forte activité dans le domaine du visible. Ces photocatalyseurs furent testés pour la dégradation de polluants modèles anionique (orange G, OG) et cationique (rouge neutre, RN) en milieux aqueux, sous irradiation artificielle UV, Visible et Solaire, ainsi que sous ensoleillement naturel extérieur. Les caractérisations multi-échelles effectuées sur les différents photocatalyseurs développés ont essentiellement démontré : - L’immobilisation par sol-gel de nanoparticules (NPs) de TiO2 et CuO sur Pal avec formation d’hétérojonctions entre ces oxydes, produisant une activité photocatalytique sous UV avérée mais toutefois trop limitée ; - La formation par précipitation de nanocomposites à base de NPs Ag2CO3 déposées sur les fibres de Pal. Selon la durée de maintien des réactifs en digestion et un protocole de cycles thermiques couplés à du vieillissement sous atmosphère de CO2, il a été possible d’obtenir Ag2CO3 sous sa forme structurale métastable hexagonale (H) et stable monoclinique (m), ou de contrôler la proportion des 2 phases dans les composites Ag2CO3/Pal. Ces nouveaux photocatalyseurs sont actifs dans le visible et les nanocomposites biphasés H+m se sont avérés plus actifs que les monophasés. - L’élaboration par mécanosynthèse de TiO2 anatase supporté sur Pal et de TiO2 principalement anatase en coexistence remarquable avec une phase monoclinique métastable B dans le cas du dopage au soufre. TiO2-S est très actif dans le visible tandis que TiO2-Pal manifeste une activité sous UV en présentant l’avantage de pouvoir exploiter les propriétés de l’argile pour développer une multifonctionnalité (photocatalyse-adsorption). Ces photocatalyseurs sont actifs sous forme de poudres dispersés et de revêtements sous irradiation solaire. La cinétique de dégradation du polluant modèle a pu être modélisée. / This work reports the development of different photocatalysts using either wet route (sol-gel and precipitation methods) or dry route (mecanosynthesis followed by annealing). The photocatalysts are TiO2 (pure or doped with sulfur) nanoparticles (NPs), TiO2 coupled with CuO and Ag2CO3 supported on natural fibrous clay from Morocco called palygorskite (Pal). The degradation of model anionic dyes (orange G, OG) and cationic dyes (neutral red, NR) in aqueous solution were investigated under artificial radiation (UV and visible) and natural sunlight. The multi-scale chemical and structural characterization and the properties investigated on the different photocatalysts showed the following results: -Immobilization of both TiO2 and CuO NPs on palygorskite by sol-gel method. Despite the heterojunctions between these functional oxides the photocatalysts exhibit a limited activity under UV irradiation. - Elaboration of nanocomposites made of Ag2CO3 NPs deposited on Pal fibers using the precipitation method. Depending on the time of reactant digestion, the number of thermal cycles and the aging for several months, Ag2CO3 adopts remarkably, in these nanocomposites, the exclusive forms of metastable hexagonal structure (H), or the stable monoclinic one (m) or a mixture of both phases with different proportions depending on the mass ratio of Ag2CO3/Pal. All Ag2CO3-Pal nanocomposites are active in the visible range for the elimination of OG. The nanocomposites in the biphasic form H + m are more active than single phases samples either in the form H or m. - Preparation of anatase TiO2 supported on Pal and TiO2 as a mixture of mainly TiO2 anatase and a minority of a remarkable monoclinic phase B by a mechanical alloying method. The NPs surfaces of these photocatalysts are acidified by grafting the sulfate groups (SO42-) and the anionic network is lightly doped with substituting O2- by S2-. These specific characteristics have made TiO2-S very active in the visible for the degradation of OG, while TiO2-Pal composite exhibits an activity under UV. Both types of photocatalysts in the form of powders dispersed in the OG solutions have proved to be active under sunlight and as well in the form of coating. TiO2-Pal has showed allows the adsorption of cationic entities RN facilitating their subsequent photodegradation.

Neste trabalho tivemos como objetivo sintetizar e caracterizar os ortossilicatos de elementos alcalino-terrosos com destaque para o Sr2SiO4, uma matriz hospedeira para íons dopantes como o cádmio II e o európio III, resultando em materiais com propriedades luminescentes. Outro objetivo é reduzir a temperatura de síntese pelos métodos aqui empregados em relação aos métodos convencionais descritos na literatura. Tanto a matriz quanto os sistemas dopados foram caracterizados por meio da difratometria de raios x, análise de área superficial e tamanho de poros, microscopia eletrônica de varredura e de transmissão. Os métodos empregados neste trabalho foram basicamente o da metátese e o do sal fundido, sendo que o método da metátese foi conduzido por sol-gel (utilizando-se sílica comercial e TEOS) e por precipitação em atmosfera ambiente e em atmosfera de nitrogênio. Já no método do sal fundido utilizamos duas temperaturas de síntese, 600 e 750ºC. A 750ºC foi utilizada uma mistura equimolar de cloreto de sódio e cloreto de potássio juntamente com nitrato de estrôncio e sílica mesoestruturada na proporção molar de 2:1. A 600ºC foi utilizada somente a mistura de nitrato de estrôncio e sílica mesoestruturada também na proporção molar de 2:1. Nestas duas formas de se conduzir a síntese por sal fundido utilizamos nitrato de sódio (proporção molar de Na/Si = 0,1) a fim de se facilitar a quebra das pontes de oxigênio da sílica e verificar a influência desse reagente sobre o produto final. Já o Ca2SiO4 e o Ba2SiO4 foram sintetizados apenas a 600ºC bem como as dopagens do Sr2SiO4 (1% em mol). Os resultados mostram uma densificação do produto em relação à sílica e a obtenção de nanofibras de silicatos obtidos pelo método do sal fundido. Já no método da metátese obtivemos carbonato de estrôncio e outros tipos de silicatos. / In this work our objective was to synthesize and characterize orthosilicates of alkaline-earth elements with emphasis on Sr2SiO4. This is a silicate host matrix for doping with ions such as cadmium II and europium III, resulting in materials with luminescent properties. Another objective is to reduce the synthesis temperature using the methods employed here when compared to conventional methods described the literature. Both the matrix and the doped systems were well characterized by X-ray diffraction, surface area and pore size distribution, scanning and transmission electron microscopy. The methods employed in this study were basically the metathesis and the molten salt; the metathesis method was conducted by sol-gel (using a commercial silica and tetraethyl orthosilicate TEOS) and precipitation in air and nitrogen atmospheres. In the molten salt method, two synthesis temperatures were used: 600 and 750ºC. At 750°C an equimolar mixture of sodium chloride and potassium chloride with strontium nitrate was used in addition to mesostructured silica in the molar ratio of 2:1. At 600°C only a mixture of strontium nitrate and mesostructured silica was used, also in the molar ratio of 2:1. In these two pathways, sodium nitrate (molar ratio Na/Si = 0.1) was used in order to facilitate the breakup of the silica oxygen bridges and its influence on the final product was also studied. Furthermore, Ca2SiO4 and Ba2SiO4 were synthesized only at 600ºC and the doping of Sr2SiO4 (1 mol %) was also carried out only at 600°C. The results show a densification of the product compared to the silica precursor and the formation of silicate nanofibers by the molten salt method. In the metathesis method we obtained strontium carbonate and other types of silicates.

Uma nova rota de síntese via metodo sol-gel para óxido de titânio (titânia) e óxido misto titânio/zircônio (zircônia) é proposta neste trabalho. As amostras foram submetidas ao tratamento hidrotérmico e obteve-se compostos mesoestruturados e de elevada área superficial. Algumas amostras foram submetidas à calcinação a 450°C para a verificação da estabilidade a altas temperaturas. As amostras foram analisadas por difratometria de raios-x (DRX), espalhamento de raios-x de baixo ângulo (SAXS), área superficial através do método BET, por microscopia eletrônica de varredura por emissão de campo (FE-SEM), além de serem testadas na fotodegradação de corantes. Foram testados diferentes alcóxidos precursores, isopropóxido de titânio e n-butóxido de titânio; ácidos, clorídrico e nítrico; e surfactantes, Pluronic® P123, Brij® 700 e Brij® 98; e também variadas as quantidades de surfactantes utilizadas, para que fosse possível analisar como estas variações afetam a síntese dos compostos e se estabelecer uma nova rota padronizada utilizando-se os melhores precursores em quantidades ideais. Para efeito de comparação, foi testada uma rota alcalina de síntese, que levou ao material com área superficial mais elevada. Como resultado deste trabalho, foi desenvolvida uma nova rota de síntese para óxidos mesoestruturados de titânio e titânio/zircônio corn elevada área superficial, na qual a etapa de calcinação para remoção do surfactante foi eliminada. Algunas dos materiais preparados mostraram excelente desempenho na degradação fotocatalítica de um corante comercial. / A new sol-gel based synthetic route for titania and mixed titania-zirconia ceramic powders is proposed in this contribution. This route combines a surfactant-template strategy with hydrothermal treatment, yielding mesostructured compoundes with a high surface area. Some samples were calcined at 450 °C in order to verify the stability of the structures at these temperatures. The materials were characterized by x-ray diffraction (XRD), small angle x-ray scattering (SAXS), surface area (BET method), field emission scanning electron microscopy (FE-SEM), and were also tested in the photocatalytic degradation of selected dyes. Different precursor alcóxidos were used: titanium isopropoxide and titanium n-butoxide. Two different acids were used to catalyze the hydrolysis reaction, HCl and HNO3. Three surfactants were used as templating agents: Pluronic P123®, Brij 700®, and Brij 98®. The amount of surfactant was also changed in order to verify how these variations affect the surface area and morphology of the resulting compounds. For comparison, an alkaline route was also tested, in which the highest surface area was observed. As a result of this work, a new synthetic route for mesostructured titania and titania-zirconia mixed oxides was developed, in which the surfactant is removed without a calcinations step, resulting in compounds with high surface areas and, in some cases, excellent photocatalytic properties for the degradation of a dye.

Neste trabalho, foi realizada a síntese de compostos do sistema PbO CrO3, em especial as composições PbCrO4 e Pb2CrO5, pelo método dos precursores poliméricos, avaliando sua aplicação como pigmentos. Para eliminar o aspecto negativo quanto à toxicidade dos materiais envolvidos, foi realizada a dispersão dos mesmos em SiO2, pelo método sol-gel. As amostras foram caracterizadas estruturalmente por difração de raios X, espectroscopia Raman e por microscopia eletrônica de varredura e transmissão. Pelos resultados de difratometria de raios X e espectroscopia Raman, foi verificado que o método dos precursores poliméricos possibilita a formação de Pb2CrO5 e PbCrO4 monofásicos para ambas as estequiometrias estudadas. Contudo, as imagens de microscopia eletrônica de varredura mostram que as partículas das duas composições apresentam forte coalescência e aglomeração. A caracterização óptica foi realizada pela técnica de reflectância difusa e coordenadas colorimétricas, em que foi determinado que as amostras de PbCrO4 possuem coloração verde-amarelada e que as amostras de Pb2CrO5 possuem coloração que varia do laranja escuro ao vermelho. A dispersão em SiO2 das partículas de Pb2CrO5 foi alcançada, no entanto, este processo provocou a formação de diferentes fases cristalinas, além de alterações na cor, as quais têm uma contribuição significativa da própria matriz SiO2, fato confirmado pela teoria de Kubelka-Munk. A incorporação dessas partículas em uma matriz polimérica de um copolímero de etileno e acetato de vinila (EVA) resultou em uma coloração homogênea da mesma, confirmando a eficácia destas partículas como pigmentos. / In this work, the synthesis of particles from the PbO-CrO3 system, in particular the PbCrO4 and Pb2CrO5 compositions were accomplished, by a polymeric precursor method, evaluating its application as pigments. In order to eliminate the negative toxic aspect of these materials, the dispersion of the same in SiO2 was achieved, by the sol-gel method. The samples were characterized structurally by X-Ray diffraction, Raman spectroscopy and scanning and transmission electron microscopy. From X-Ray diffraction and Raman spectra results it was verified that the polymeric precursors method is able to form single phase Pb2CrO5 and PbCrO4 for both studied stoichiometries. Although, scanning electron microscope images revealed that both compositions present strong coalescence and agglomeration of the particles. Optical characterization was carried out by diffuse reflectance technique and colorimetric coordinates. It was verified that the PbCrO4 samples possess green-yellowish coloration and the Pb2CrO5 samples presents coloration that varies from dark orange to red. The dispersion of Pb2CrO5 particles in SiO2 was reached, however, this process causes the formation of different crystalline phases, besides alteration in color, which have a significant contribution from the SiO2 matrix, confirmed by Kubelka-Munk theory. The incorporation of these particles in a polymeric matrix of ethylene vinyl acetate copolymer (EVA) resulted in the coloration of the same, confirming the efficiency of these particles as pigments.