Ao longo do tempo, os revestimentos de fachada permanecem expostos a diversos agentes de degradação, sejam eles associados aos próprios materiais empregados ou a fatores externos. Tal exposição implica em manchas formadas a partir da deposição de partículas poluentes na superfície dos revestimentos, elevando seus custos para limpeza e manutenção. Uma vez que permanecem expostas à radiação solar, as fachadas se mostram atraentes ao uso de materiais fotocatalíticos, os quais catalizam a mineralização de agentes poluentes, transformando-os em produtos inócuos. A adição de dióxido de titânio (TiO2) a argamassas e concretos de cimento branco desenvolve superfícies autolimpantes, reduzindo a formação de manchas e mantendo sua coloração original ao longo do tempo. No entanto, a eficiência e a economia no uso de materiais fotocatalíticos em aplicações reais é fortemente afetada pela disponibilidade da radiação ultravioleta adequada para ativá-los. Portanto, o presente trabalho busca avaliar a capacidade autolimpante de argamassas e coberturas fotocatalíticas de TiO2 expostas a diferentes configurações de posicionamento no microclima urbano da cidade de Porto Alegre. Para isto, foram confeccionadas amostras de argamassa e coberturas de pasta ou argamassa contendo diferentes teores de TiO2, as quais foram manchadas com Rodamina B e lodo de cinzas da queima de eucalipto e, a seguir, expostas sob diferentes condições de posicionamento, voltadas para as orientações norte, sul, leste e oeste, à 0º, 45º e 90º. Ao longo do período de exposição, foram realizadas leituras cromáticas (sistema CIELab) na superfície das amostras, tendo em vista a descoloração dos manchamentos aplicados. Para aquelas manchadas com Rodamina B, a degradação do corante se mostrou mais eficiente nas argamassas com maiores teores de TiO2 e nas configurações de posicionamento que recebem maior incidência de radiação solar. As coberturas de pasta apresentaram valores mais elevados de variação de cor (ΔE) e refletância (L*), na comparação à aplicação do TiO2 como cobertura de argamassa ou incorporado à mistura − métodos os quais se mostraram resultados equivalentes. / Building façades are commonly exposed to polluting agents generated by vehicles and industries exhausts, which cause stains on their surfaces and increase efforts and costs both for cleaning and maintenance. Facades are attractive to photocatalytic materials usage, which transform pollutants to innocuous products. The addition of titanium dioxide (TiO2) to white cement mortars and concretes develops self-cleaning surfaces which are capable to reduce stains and maintain their original color along the time. However, efficiency and economy in the use of photocatalytic materials in real applications are strongly affected by the availability of suitable ultraviolet radiation to activate them. This thesis aims to evaluate the self-cleaning ability of TiO2-containing mortars and coatings (paste or mortar) exposed to controlled positioning settings in the urban environment of Porto Alegre, Brazil. Mortars and coatings were prepared containing different additions of TiO2 and then were soiled by Rhodamine B (RhB) or burning ashes of eucalyptus sludge. Samples were exposed under outdoor conditions facing north, south, east and west orientations, 0º, 45º or 90º slopes. During the exposure test, discoloration effect on samples' surface was monitored by colorimetric measurements (CIELab color space) using a portable spectrophotometer. A final analysis was performed at the end of the measurements, including statistical tests. Self-cleaning ability was better seen both for higher additions of TiO2 and settings which receive higher intensities of solar radiation. Cement paste coatings showed higher values both of color change and reflectance when compared to mortar coatings or TiO2 added to the mixture − which performed equivalent results.

A fotocatálise heterogênea é um processo que apresenta baixa seletividade de degradação. Nesse sentido, a síntese de materiais dotados de impressão molecular (IM) deve ajudar a contornar este problema. Os fotocatalisadores dotados de IM foram sintetizados de acordo com duas classes: uma inorgância (via diferentes rotas sol-gel e TEOS como percursor de sílica) e outra orgânica (via impressão não-covalente por precipitação e ácido metacrílico como monômero). No caso da primeira, a impressão molecular foi investigada através do uso de corante (rodamina B) e diferentes fármacos como template (substrato molde). No caso da matriz orgânica, o fármaco diclofenaco foi usado como molécula template. Os materiais foram caracterizados por análises texturais, estruturais e morfológicas. Com respeito à matriz à base de sílica, os sistemas com maiores valores de área específica foram observados pela rota ácida. Como efeito da rota, foi observado que a rota ácida apresentou um fator de seletividade 47% maior que a rota não-hidrolítica em testes de adsorção seletiva. Os resultados obtidos por análise de isotermas também convergem no sentido de revelarem que a rota ácida apresentou a maior capacidade de adsorção (997,9 mg/g) dentre as diferentes rotas de síntese pelo método sol-gel. Nos ensaios de fotocatálise (rodamina como template), foi conseguido um aumento de seletividade e competitividade na fotodegradação da rodamina de até 187% e 290%, respectivamente, comparado ao P25 (amostra comercial de TiO2). Quanto ao uso de fármacos como template em matriz inorgânica, os fotocatalisadores com impressão molecular obtiveram um aumento na adsorção e fotodegradação de até 751 e 427%, respectivamente, em comparação ao P25. Os materiais baseados em matriz orgânica também apresentaram seletividade em comparação ao P25. O valor médio do coeficiente de seletividade (estimado a partir da degradação de moléculas não-alvo, a fluxetina e o paracetamol) foi estimado em 2,8 – portanto sugerindo que a presença de cavidades tridimensionais é um dos principais fatores da seletividade observada. Com o objetivo de explorar o potencial de adsorção das cavidades de impressão molecular, os estudos dos fotocatalisadores seletivos com adição de P25 foram conduzidos de maneira a manter baixa a concentração de TiO2 (de 7 a 44 mg/L em cada teste fotocatalítico). Estudos de reuso do fotocatalisador (com e sem regeneração) também foram conduzidos. Tanto os materiais de matriz inorgânica como orgânica mantiveram em pelo menos 60% da eficiência fotocatalítica original após vários ciclos. / Heterogeneous photocatalysis is a process that has a low selectivity for degradation. In this sense, the synthesis of materials with molecularly imprinting (MI) should help to overcome this problem. The photocatalyst containing MI was synthesized according to two classes: An inorganic one (via different sol-gel routes and TEOS as silica precursor) and an organic one (via non-covalent imprinting by precipitation having methacrylic acid as monomer). In the first case, MI was investigated by use of the dye (rhodamine B) and several pharmaceutical compounds as template. In case the organic matrix, diclofenac was used as the template molecule. The samples were extensively characterized by textural, structural and morphological analysis. With respect to the silica-based matrix, the systems with larger surface area values were obtained by acid route. As effect of the route, it was observed that the acid route showed a selectivity factor 47% higher than that of the non-hydrolytic route in selective adsorption tests. Among the different synthesis routes prepared by sol-gel method, the isotherms analysis showed that acid route has the highest adsorption capacity (997.9 mg/g). Compared to the P25 (commercial sample of TiO2), the photocatalysis assays (rhodamine as the template) have shown an increase in selectivity and competitiveness up to 187% and 290%, respectively. Regarding the use of pharmaceutical as template in the inorganic matrix, the imprinted photocatalyst had an increase in adsorption and photodegradation up to 751 and 427%, respectively. The systems based on the organic matrix have also showed selectivity compared to the P25. The mean value of selectivity coefficient for degradation (estimated from the non-target molecules, such as fluoxetine and paracetamol) was estimated to be 2.8 – thus, suggesting that the presence of three-dimensional cavities is a major factor in the observed selectivity. In order to explore the full potential of adsorption from the MI cavities, the photocatalyst containing P25 were prepared with the low concentration of TiO2 (from 7 to 44 mg/L in each photocatalytic test). The reuse of photocatalysts (with and without regeneration) was also studied. Both inorganic and organic matrix retained at least 60% of the original efficiency after several cycles.

Orientadora: Telma Teresinha Berchielli / Banca: Izabelle Auxiliadora Molina de Almeida Teixeira / Banca: Paulo Henrique Moura Dian / Resumo: Os objetivos foram avaliar diferentes formas de dosagem de indicadores (infusão contínua 24h, e duas doses diária de indicador) e verificar sua precisão e acurácia para estimativa do fluxo duodenal de matéria seca (MS), consumo de concentrado, consumo de volumoso, produção fecal e digestibilidade aparente da MS em bovinos. No experimento 1, seis animais receberam os indicadores Cr-EDTA e YbCl3 através de uma bomba de infusão contínua, via fístula ruminal durante seis dias de adaptação nos dois períodos de 17 dias, enquanto os outros seis animais receberam os mesmos indicadores em duas dosagens diárias (8h e às 19h). No experimento 2, doze animais receberam os indicadores Cr-EDTA, YbCl3, LIPE®LÍQUIDO, FDNi e FDAi, em duas doses diárias que foram utilizados nas estimativas do fluxo duodenal de matéria seca (MS) pelo método de único e duplo indicador. Os indicadores TiO2 e LIPE®LÍQUIDO foram utilizados para estimativa do consumo de concentrado, produção fecal, digestibilidade aparente e os indicadores internos, FDNi e FDAi para estimar consumo de volumoso, produção fecal e digestibilidade. No experimento 1, o delineamento utilizado foi inteiramente casualisado em parcelas subdivididas com dois tratamentos em dois períodos. No experimento 2, o delineamento foi o de blocos em parcelas subdivididas. As médias foram comparadas pelo teste tukey a 5%. No experimento 1 não foram observadas diferenças entre as formas de fornecimento dos indicadores (P>0,05). No experimento 2, a FDNi estimou o fluxo de digesta no duodeno e a produção fecal e o consumo de volumoso. A estimativa do consumo de volumoso através do FDNi e FDAi foram semelhantes ao observado (P>0,05). O TiO2 e LIPE®LÍQUIDO foram acurados na estimativa do consumo de concentrado / Abstract: The objectives of this study were to evaluate by two metabolism trials different ways to dose markers (by continuous infusion for 24 hours and by two doses of marker per day) and also to study the accuracy and reliability of differents markers to estimate duodenal flow of nutrients concentrate intake, roughage intake, fecal production and apparent digestibility of dry matter (DM) in cattle. Twelve crossbred heifers were used in both experiments with average body weight of 361.7kg ± 59 and approximately 24 months of age, cannulated in the rumen and duodenum. In experiment 1, six animals received the markers Cr-EDTA, YbCl3 by continuous infusion via ruminal fistula in two periods of 17 days, while the other six animals received the same markers in twice daily dosing (8 and 7hours). In experiment 2, animals received the twelve markers twice daily during the experimental periods. Markers Cr-EDTA, YbCl3, LIPE®LIQUID, iNDF and iADF were used in the estimation of duodenal flow of nutrients by the method of single and double markers. Markers TiO2 and LIPE®LIQUID were used to estimate concentrate intake, fecal output, digestibility of DM and internal markers, iNDF and iADF to estimate forage intake, digestibility and fecal production. In experiment 1, a split plot design was used with two treatments (supply), six replicates in two periods. In experiment 2, the experimental design was randomized blocks in split plots, where the markers were considered as treatments. In both experiments, the means were compared by Tukey test at 5%. In experiments 1, there were no differences between the ways to supply the marker (P>0.05). In experiment 2, the iNDF was the best variable to predict digest flow in the duodenum and fecal production. iNDF and iADF were not d significantly different when the average intake of roughage were compared with the observed. The TiO2 was not significantly different... (Complete abstract click electronic access below) / Mestre

This final thesis goal has been to try and develop a titanium dioxide coating for water purification. The coating should be used in a manufacturing industry on textiles. Water purification is achieved through photocatalysis with titanium dioxide and UV-radiation, where hydroxyl radicals form through oxidation. The kind of textile fiber chosen for the substrates is a polyester fiber. The substrates have been developed in several different shapes. Two different knitted patterns was developed, one flat patterned and one wavy patterned. Another kind of substrate was a spacer-type and there was also a substrate made from a PET-bottle. The different substrates were chosen to compare the different coatings effect on different surfaces and the different coatings were developed from two types of titanium dioxide. The coated substrates have been analyzed for hydroxyl radical generating properties. By testing a sample of water with titanium dioxide against a sample with water that had no additives, it was shown that titanium dioxide generates more hydroxyl radicals. The results of the work showed that the recipe containing 3 % titanium dioxide and 3 % acrylic binder showed good properties for water purification. In addition, the results showed a stronger effect for the wavy patterned substrate then the flat patterned, which is an interesting result that should be researched further in the future. / Program: Textilingenjörsutbildningen

[pt] O Brasil é um dos produtores mundiais de materiais contendo vanádio, exportando cerca de 10 t/ano, na forma de seu óxido mais comum, V2O5, o qual ocorre associado à magnetita. O seu processo de produção industrial tem como primeira etapa a concentração deste mineral, onde é gerado uma grande quantidade de rejeito, o qual se estima conter entre 5 por cento –15 por cento de titânio e cerca de 30 por cento de ferro. Materiais com estas características podem viabilizar uma fonte para a recuperação do titânio por processos químicos que viabilizem a separação seletiva dos seus constituintes. Desta forma, inicialmente foi realizada a caracterização de um rejeito mineral por métodos convencionais: distribuição granulométrica; DR-X; FR-X; Microscopia Eletrônica de Varredura e ICP-OES. Em seguida, foi conduzida uma avaliação termodinâmica de possíveis reações com diferentes agentes químicos em condições de variação de temperatura. As reações ocorreram em um forno do tipo mufla, utilizando barquetes cerâmicos. Após a reação e eventual fusão, a amostra era imergida água destilada aquecida, em seguida filtrada e seca, e o material sólido filtrado era então submetido a HCl 5 por cento aquecido, em seguida filtrado e seco. A caracterização dos produtos foi feita de maneira semelhante ao do material inicial. O resultado da distribuição granulométrica determinou tamanho médio de partícula de 96 micrômetros. A análise quantitativa de DR-X indicou 25 por cento de óxidos de titânio e o restante de minerais complexos como Tremolita e Clinocloro llb-2. A análise do FRX inicial apontou presenças de Na2O, MgO, Al2O3, SiO2, SO3, K2O, CaO, MnO, 11,3 por cento de TiO2, e 25,8 por cento de Fe2O3. A análise termodinâmica indicou a potencial formação de produtos solúveis em água contendo Al e Si enquanto o Ti se agrega a um composto insolúvel. O Fe pode ser solubilizado na etapa seguinte com HCl, onde as solubilizações foram, nitidamente, maiores. Observou-se a formação de um produto cristalino, prevalecendo a forma CaTiO3, com o desaparecimento das fases originais, em um dos ensaios. Os resultados também indicaram que as perdas de massa foram crescentes nas etapas de solubilização com o aumento da temperatura e da relação mássica, implementadas na ustulação sólido-sólido, contudo foram gerados produtos complexos que dificultaram a concentração do teor Ti. Em linhas gerais, o processo selecionado indicou a viabilidade de solubilizações seletivas, as quais geram um produto final com maior teor de titânio que o inicial e razoável recuperação deste metal, se fazendo necessário otimização do processo. / [en] Brazil is one of the world producers of materials containing vanadium, exporting about 10 ton/year, in the form of its most common oxide, V2O5, which occurs in association with magnetite. Its industrial production process has as its first step the concentration of this mineral, where a large amount of tailings is generated, which composition is estimated between 5 percent -15 percent titanium and about 30 percent iron. Materials with these characteristics can provide a source for the recovery of titanium by chemical processes that enable the selective separation of its constituents. In this way, the characterization of a mineral tail was initially performed by conventional methods: granulometric distribution; DR-X; FR-X; Scanning Electron Microscopy and ICP-OES. Then, a thermodynamic evaluation of possible reactions with different chemical agents under conditions of temperature variation was carried out. The reactions occurred in a muffle furnace, using ceramic caskets. After reaction and eventual melting, the sample was immersed heated distilled water, then filtered and dried, and the filtered solid material was then subjected to heated 5 percent HCl, then filtered and dried. The characterization of the products was done in a similar way to the starting material. The result of the particle size distribution determined a mean particle size of 96 micrometers. Quantitative analysis of DR-X indicated 25 percent of titanium oxides and the rest of complex minerals such as Tremolita and Clinochlore IIb-2. Initial FRX analysis showed Na2O, MgO, Al2O3, SiO2, SO3, K2O, CaO, MnO, 11.3 percent TiO2 and 25.8 percent Fe2O3presentations. Thermodynamic analysis indicated the potential formation of water-soluble products containing Al and Si while Ti is added to an insoluble compound. Fe can be solubilized in the next step with HCl, where the solubilizations were markedly larger. It was observed the formation of a crystalline product, prevailing the CaTiO3 form, with the disappearance of the original phases, in one of the tests. The results also indicated that mass losses were increased in the solubilization steps with the increase in temperature and mass ratio, implemented in solid-solid roasting, however complex products were generated which hindered the concentration of Ti content. The selected process indicated the feasibility of selective solubilizations, which generate a final product with higher titanium content and reasonable recovery of this metal, making process optimization necessary.

Introdução: O dióxido de titânio (TiO2) é um corante encontrado na forma de partículas em diversos produtos industrializados. Muitos estudos, a maioria envolvendo o trato respiratório, alertam sobre os efeitos prejudiciais advindos da exposição ao TiO2. Embora partículas da dieta, tais como o TiO2, sejam ingeridas diariamente, ainda existem poucos estudos investigando seus efeitos sobre o trato gastrointestinal. Objetivos: O objetivo principal desse trabalho é investigar a ação de nano (NP) e micropartículas (MP) de TiO2 sobre a resposta inflamatória no intestino delgado de camundongos. Material e Métodos: Camundongos Bl 57/6 foram divididos em 2 grupos experimentais, os quais receberam NP TiO2 (66 nm) ou MP TiO2 (260 nm) a uma dose de 100 mg/Kg/dia, e um grupo controle, o qual recebeu água destilada. O tratamento foi administrado por gavagem, durante 10 dias, uma vez ao dia. Ao final, o intestino delgado foi coletado para a análise de citocinas (IL-1b, IL-4, IL-6, IL-8, IL-10, IL-12, IL-13, IL-17, IL-23, TNFa, IFNg e TGFb) por ELISA e quantificação de células T CD4+, T CD8+, células dendríticas e natural killers por imunohistoquímica. Resultados: Os resultados demonstram maior concentração de citocinas IL-12, TNFa, IFNg, IL-4, IL-23 e TGFb, e células T CD4+ nos grupos que receberam TiO2. O aumento de citocinas foi mais importante no íleo, onde há maior concentração de células M, as quais representam a principal via de captação de partículas no intestino. Conclusão: As partículas de TiO2 provocaram uma resposta pró-inflamatória, predominantemente do tipo Th1, no intestino delgado dos camundongos, especialmente no íleo. Esses dados representam uma evidência in vivo do potencial inflamatório de partículas de TiO2 sobre o trato gastrointestinal / Introduction: Titanium dioxide (TiO2) is a white pigment widely found as micro and nano-sized particles added to food, drugs, cosmetics, etc. Studies involving the pulmonary tract warn about adverse effects resulting from exposure to TiO2, emphasizing its inflammatory potential. Although the gastrointestinal tract is considerably exposed to TiO2 particles at daily basis there are few information regarding its adverse effects on intestine. Objectives: We aimed to investigate the effects of TiO2 nanoparticles (NP) and microparticles (MP) on inflammatory response in the small intestine of mice. Methods: Bl 57/6 mice received suspensions containing TiO2 (100 mg/Kg/day) as TiO2 NP (66 nm), or TiO2 MP (260 nm) by gavage for 10 days, once a day; control group received only distilled water. At the end of the treatment, the small intestine were extracted for assessment of cytokines (IL-1b, IL-4, IL-6, IL-8, IL-10, IL-12, IL-13, IL-17, IL-23, TNFa, IFNg e TGFb) by ELISA and quantification of inflammatory cells (T CD4+, T CD8+, dendritic cells, and natural killer) by immunohistochemistry. Results: We found increased levels of T CD4+ cells and cytokines (IL-12, TNFa, IFNg, IL-4, IL-23, and TGFb) on groups receiving TiO2 when compared to control group. Cytokines production was more important on the ileum, local presenting greater concentration of M cells, which represent the main pathway of particles uptake on gut. Conclusion: Our findings indicate that TiO2 particles induce a Th1 mediated inflammatory response on small bowel in mice. These results represent an in vivo evidence of the inflammatory potential of TiO2 particles on the gastrointestinal tract

L’objet de cette thèse est le développement et l’étude de la photoréactivité de TiO2, absorbant dans le visible et ayant des propriétés autonettoyantes et de dépollution de l’eau et de l‘air. Dans ce contexte, des films d’épaisseur controlée et mésostructurés de TiO2 non dopés et dopés par différents métaux (platine, vanadium et tungstène) , ont été synthétisés par voie sol-gel combinée au procédé d'auto-assemblage induit par évaporation. Les propriétés structurales et optiques ainsi que la composition chimique de la surface des films ont été caractérisées par de nombreuses techniques de caractérisation telles que DRX, GISAXS, TEM, MEB ellipsoporosimétrie, DRUV et XPS. Une étude complète des propriétés photocatalytiques des films à base de TiO2 aux interfaces solide-solide, solide-liquide et solide-gaz a été réalisée en utilisant respectivement les tests avec de l’acide stéarique, du bleu de méthylène et de l’acétone. Durant cette étude, nous avons montré qu’un contrôle adapté de l’épaisseur des films, de la nature et de la quantité du dopant peut améliorer l’activité photocatalytique jusqu’à un facteur de 16 par rapport à des films non dopés. Des tests préliminaires de piégeage chimiques des radicaux OH• par l’acide téréphtalique sous irradiation UV ont montré qu’il existait une bonne corrélation entre la photoréactivité et la génération des radicaux OH•. / The aim of this thesis is the development and study of photocatalytic properties of visible light photoactive mesoporous TiO2-based films to act as self-cleaning, and purification systems applied to air and water. Pure and doped mesoporous titania films with different metals as Pt, V and W were prepared by sol-gel method combined with evaporation induced self-assembly process at different thicknesses. Structural, optical properties and chemical composition of these films were characterized by XRD, GISAXS, TEM, SEM, ellipsoporosimetry , DRUV and XPS. In order to better characterize and compare the efficiency of these films at solid-solid, liquid-solid and air-solid interfaces, several tests were used: mineralization of stearic acid, photobleaching of methylene blue and photooxidation of acetone. In this study, it is shown how a suitable control of the film thickness, the nature and amount of the dopant can improve the photocatalytic activity up to a factor of 16 relative to un-doped films. Preliminary results on the OH• radicals production using terephtalic acid as a chemical probe showed good correlation between photoreactivity and generation of these radicals.

Hunting for improved energy storage devices based on rechargeable Li-ion batteries and other advanced rechargeable batteries is one of the hottest topics in today's society. Both Li- ion batteries and Li-O2 batteries have been studied within the thesis. The research work of this thesis contains two different parts. Part 1. The controlled synthesis of the extreme small sized nanoparticles and their application for Li-ion batteries; Part 2. The study of the O2 reduction mechanism in Li-O2 batteries with aprotic electrolytes. In the first part, two different types of extremely small-sized TiO2 nanoparticles with at lease on dimension less than 3 nm was synthesised via solvothermal/hydrothermal reaction, i.e., anatase nanosheets and TiO2(B). These nanoparticles were obtained without any contamination of long chain organic surfactants. A series of systematic characterisation methods were employed to analyse the size, phase purity, and surface condition. These extremely small-sized nanoparticles exhibit improved capacity, rate performance as anode materials for Li-ion batteries. The shapes of load curves of charge and discharge are significantly modified due to the reduced size of TiO2 nanoparticles. In chapter 3, we will see the variation of the capacity and the load curve shape of the anatase nanosheets according to their thickness and surface conditions. The origin of the excessive capacity is analysed based on the electrochemical data. It has been identified that both pseudocapacitive (interfacial) Li+ storage and the excessive Li+ -storage from the bulk contribute to the increased capacity. In chapter 4, the shape and size of the sub-3 nm TiO2(B) nanoparticles are studied, a method based the PXRD data is established. These nanoparticles demonstrate a reversible capacity of 221 mAh/g at a rate of 600 mA/g and remain 135 mAh/g at 18000 mA/g without significant capacity fading during cycling. In the last part, a systematic study of O2 reduction mechanism for aprotic Li-O2 batteries based on the combination of a series of electrochemical and spectroscopic data is presented. The novel mechanism unifies two previous models for the growth of Li2O2 during discharge, i.e., Li2O2 particle formation in the solution phase and Li2O2 film formation on the electrode surface. The new mechanism provides fundamental conceptions for the improvement of Li2O2 batteries and shed light on the future research of Li2O2 batteries.

Amostras de titânia foram sintetizadas por seis rotas diferentes: quatro pelo método sol-gel, utilizando condições e precursores distintos, por combustão de solução líquida e pelo método Pechini. Após tratamento térmico que variou de 100°C a 900°C, as amostras foram analisadas por difratometria de raios X, termogravimetria e pelo método BET de obtenção de áreas superficiais específicas. As amostras obtidas por sol-gel utilizando como precursores o isopropóxido de titânio (Pro) e o n-butóxido de titânio (But) geraram materiais de elevada área superficial, com alta fração molar de anatase e sem resíduos a 500°C. As amostras obtidas por sol-gel com excesso de íon peptizante (Nan) possuiam também altas áreas superficiais, além de estabilizarem a fase anatase a até 500°C, com resquícios de bruquita. As amostras obtidas por sol-gel utilizando um surfactante não iônico (Sur) demonstraram as maiores áreas superficiais, os menores tamanhos de cristais e estabilidade de anatase pura a 500°C. Esses materiais têm, pois, potencial para aplicação em fotocatálise, em células solares sensibilizadas por corantes e em células a combustível, entre outras. Os métodos da combustão (Com) e de Pechini (Pec) geraram produtos de baixa área superficial e com baixa ou com nenhuma fração de anatase. Porém, são métodos simples e eficientes de obtenção de titânia para aplicações que não necessitem da anatase como fase única. / Titania samples were prepared by six different routes, four of them by the sol-gel method using different precursors and reaction conditions, a solution combustion route and a Pechini method route. After thermal treatment ranging from 100 C to 900 C, the resulting materials were analyzed by X-ray diffraction, thermogravimetric analysis and surface area determination (BET method). The materials obtained by the sol-gel method using titanium isopropoxide (Pro) and titanium n-butoxide (But) as precursors yielded ceramics with high surface area, a high anatase molar fraction, without residues when heated at 500 C. Samples obtained by the sol-gel route using excess peptization agent (Nan) also showed high surface areas and yielded anatase with traces of brookite which was stable up to 500 C. Samples obtained using the sol-gel route with non-ionic surfactant (Sur) exhibit the highest surface area, smallest crystallite sizes and stable anatase with traces of brookite up to 500 C. These materials have, therefore, potential application in the areas of photocatalysis, dye- sensitized solar cells and fuel cells, among others. The combustion (Com) and Pechini (Pec) methods yielded materials with low surface area, with little or no presence of anatase. They are, however, simple and efficient methods for obtaining pure titania when the pure form of anatase is not a necessity.

A range of titanium dioxide (titania) samples provided by Huntsman Pigments and Additives were investigated for their suitability for use in various optoelectronic devices, specifically dye-sensitized solar cells (DSSCs). Five of the titania samples are 1-20 micrometre size spherical 3D porous beads made up of titania nanoparticles and a further six samples are porous titania nanoparticle clusters of no specific shape, all of which possess high surface areas from 85 to 276 m2g-1. The samples were compared to commercially available nanocrystalline TiO2 powders and paste. All of the samples were initially assessed for suitability in DSSC devices by investigating various properties such as crystal phase, particle size, band gap, morphology and N719 dye adsorption, both as a powder sample and as a sintered film, employing techniques such as powder x-ray diffraction, UV/Vis spectroscopy and scanning electron microscopy. Different methods of formulating the samples into pastes for application to a substrate were attempted and electrochemical properties of a selection of films were also compared. The more promising titania samples were formulated into dye-sensitized solar cells and cell efficiencies calculated. DSSC devices were also fabricated with low temperature (125oC) sintering of the titania layer to assess the suitability of the samples for use in devices with flexible substrates. Initial devices incorporating the Huntsman TiO2 samples provided low efficiencies (< 0.1%). The samples were then modified with pre-sintering treatment prior to paste formulation to optimize crystallinity, particle size, porosity and surface area. The modified titania bead samples showed great promise in low temperature sintered devices, providing device efficiencies of 2.8%, more than double that of those incorporating the standard P25 TiO2 (1.3%). After sample modification a superior solar cell performance (3.2%) was also observed in 510oC sintered devices when compared to the standard P25 TiO2 devices (2.9%), with higher photocurrent and open circuit voltage than devices fabricated from commercially optimized TiO2 paste. Devices were also fabricated using pre-sensitized titania in an attempt to reduce device manufacturing time. The modified samples again showed good performance, providing working devices with efficiencies comparable to the equivalent pre-sensitized P25 devices.