Thesis (Ph. D.)--Michigan State University. Dept. of Chemistry, 2006. / Title from PDF t.p. (viewed on June 19, 2009) Includes bibliographical references. Also issued in print.

Thesis (M.S. in Physics)--United States Naval Postgraduate School, 1959. / "Physics and Mathematics" -t.p. Includes bibliographical references (p. 33).

Thesis--University of California, Berkeley, 1959. / "Physics and Mathematics" -t.p. Includes bibliographical references (p. 129-130).

Thesis (Ph. D.)--University of Texas at Austin, 2005. / Vita. Includes bibliographical references.

The basis of prosperity of 20th centrury is oil. As oil is going to be used up, people need to find alternatives to meet the earth’s energy demand in 21st centrury. For each second, there are about 1.2×1017 J energy hitting the earth. The energy in 1 hour of sunlight is about 4.32×1020 J, which almost meets the energy consumed on earth in 2016. It determines solar energy may be a potential candidate to solve the energy crisis. As for techniques to utilize solar energy, the most popular one is using photovoltaic (PV) cells. PV cell is a device to convert solar energy into electricity. There are also some other techniques trying to utilize solar energy. Photocatalysis is one of them, which is to convert solar energy into chemical energy. Applications of photocatalysis have extended from hydrogen evolution via water splitting to environemtnal remediation, CO2/ N2 reduction and so on. Photocatalysis, as an advanced oxidation process, has been extensively studied and applied to the purification and remediation of contaminated water and wastewater, and exhibits advantages over conventional treatment technologies. When considering solar energy as an energy source for photocatalysis, it is key to prepare visible light-responsive materials. Bismuth-based semiconductors are promising materials as visible light-responsive photocatalysts primarily due to their suitable band gaps, well-dispersed valence bands, and commercial availabilities at reasonable costs, as well as the possibility of preparing them under mild conditions. Recent work focusing on the preparation, characterization and activity testing of bismuth-based photo-active materials as well as their associated photoreactor designs are introduced herein. In order to enhance the photocatalytic activities of the new materials, different precursors, additives, preparation procedures and process parameters, as well as surface treatments were explored to obtain binary and ternary heterostructures, with different doping, surface modification, nanoparticle sizes and morphologies. It was found that formation of heterojunction and loading metal nanoparticle on the surface are very effective to imrove the photocatalytic activity of the support. In this work, we found that palladium nanoparticles modified BiVO4 exhibited excellent activity in the decomposition of phenol, which was even higher than TiO2. To facilitate the separation process of catalysis particels from a slurry system, magnetically separable composites were also prepared, and it was found that it is very effective to remove the particles from the slurry system using external magnets. To further scale up this process, two different types of immbolized photoreactors (flat-plate and packed beads photoreactor) were also developed. Suggestions were made for further work in this research area.

Neste trabalho foram empregados os métodos hidro e solvotérmico para sintetizar três diferentes catalisadores à base de bismuto (Bi2WO6, BiOI e BiVO4), visando aplicação em fotocatálise heterogênea sob radiação visível. Foram investigadas as influências do tempo de síntese, da calcinação, da adição de polivinilpirolidona (PVP) e do tipo de solvente usado durante a síntese sobre a morfologia, cristalinidade, área superficial específica e band gap das amostras. Os catalisadores foram caracterizados por microscopia eletrônica de varredura (MEV), espectroscopia de refletância difusa (ERD), difração de Raios-X (DRX) e adsorção de N2. Para avaliar a atividade fotocatalítica das amostras sintetizadas foram realizados experimentos em um reator batelada agitado, com o catalisador em suspensão e uma lâmpada de LED como fonte de radiação visível. As moléculas testes escolhidas foram o corante rodamina B, para determinação das amostras com maior atividade e, posteriormente, o fármaco prednisolona, sendo então estudados a influência da concentração de catalisador e do pH inicial do meio reacional. Foram realizados, também, ensaios de toxicidade com o organismo Lactuca sativa – sementes de alface, para avaliar a toxicidade da prednisolona pura, da mistura água e catalisador de BiOI e das alíquotas provenientes da reação de degradação da prednisolona após diferentes tempos. As amostras de Bi2WO6 apresentaram boa cristalinidade e semelhanças morfológicas apesar dos diferentes tratamentos. As amostras de BiOI, por sua vez, apresentaram diferenças significativas de morfologia, de microesferas para microplacas, quando foi feita a mudança de solvente e a amostra de BiVO4 apresentou um formato de paralelepípedo. Nos testes fotocatalíticos com a rodamina B, o catalisador que se mostrou mais ativo foi o BiOI cuja síntese continha PVP e etilenoglicol (kap = 0,0207 min-1) e o BiVO4 foi o que apresentou a menor atividade (kap = 0,0013 min-1). Na degradação da prednisolona, a maior taxa de degradação foi obtida com 1 g L-1 de catalisador e no pH natural do fármaco, 6,8. Os ensaios de toxicidade revelaram que nem a prednisolona nem a mistura água e catalisador são tóxicas para as sementes de alface, as alíquotas provenientes da reação, porém, tiveram um aumento de sua toxicidade com o aumento do tempo de reação. / In this work, solvo and hydrothermal methods were applied to synthesize three types of bismuth catalysts (Bi2WO6, BiOI and BiVO4) aiming to the apply it in heterogeneous photocatalysis under visible light. Were investigated the influences of reaction time, calcination, addition of poly (vinyl pyrrolidone) (PVP) and the solvent type during synthesis on their morphology, crystallinity, surface area and band gap. The catalysts were characterized by scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD) and nitrogen adsorption/desorption. To evaluate photocatalytic activity of the synthesized samples, experiments were carried out in a stirred batch reactor, with the catalyst in suspension and a LED lamp as a source of visible light. The test molecules chosen were the rhodamine B dye for determination of the samples with higher activity and subsequently the drug prednisolone, and then was studied the effect of catalyst concentration and initial pH of the reaction medium. Toxicity tests were also perfomed with organism Lactuca sativa – lettuce seeds, to the toxicity of pure prednisolone, water and BiOI catalyst mixture and aliquots from prednisolone degradation after different reaction times. As a result, the Bi2WO6 samples presented good crystallinity and morphological similarities despite having undergone different treatments. The BiOI catalysts presented a significant difference in morphology, microspheres to microplates, when changed the solvent, while the BiVO4 sample presented a parallelepiped shape. In the photocatalytic tests with rhodamine B, the catalyst with the highest activity was BiOI, containing PVP and ethylene glycol (kap = 0.0207 min-1) in its synthesis, and the BiVO4 was the catalyst with the lowest activity (kap = 0.0013 min-1). In the prednisolone degradation, the highest degradation rate was obtained with 1 g L-1 of catalyst and natural pH of the drug, 6.8. The toxicity tests showed that neither prednisolone nor water and catalyst mixture are toxic to lettuce seeds, aliquots from reaction, however, had an increase in their toxicity with increasing reaction time.

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Neste trabalho foram empregados os métodos hidro e solvotérmico para sintetizar três diferentes catalisadores à base de bismuto (Bi2WO6, BiOI e BiVO4), visando aplicação em fotocatálise heterogênea sob radiação visível. Foram investigadas as influências do tempo de síntese, da calcinação, da adição de polivinilpirolidona (PVP) e do tipo de solvente usado durante a síntese sobre a morfologia, cristalinidade, área superficial específica e band gap das amostras. Os catalisadores foram caracterizados por microscopia eletrônica de varredura (MEV), espectroscopia de refletância difusa (ERD), difração de Raios-X (DRX) e adsorção de N2. Para avaliar a atividade fotocatalítica das amostras sintetizadas foram realizados experimentos em um reator batelada agitado, com o catalisador em suspensão e uma lâmpada de LED como fonte de radiação visível. As moléculas testes escolhidas foram o corante rodamina B, para determinação das amostras com maior atividade e, posteriormente, o fármaco prednisolona, sendo então estudados a influência da concentração de catalisador e do pH inicial do meio reacional. Foram realizados, também, ensaios de toxicidade com o organismo Lactuca sativa – sementes de alface, para avaliar a toxicidade da prednisolona pura, da mistura água e catalisador de BiOI e das alíquotas provenientes da reação de degradação da prednisolona após diferentes tempos. As amostras de Bi2WO6 apresentaram boa cristalinidade e semelhanças morfológicas apesar dos diferentes tratamentos. As amostras de BiOI, por sua vez, apresentaram diferenças significativas de morfologia, de microesferas para microplacas, quando foi feita a mudança de solvente e a amostra de BiVO4 apresentou um formato de paralelepípedo. Nos testes fotocatalíticos com a rodamina B, o catalisador que se mostrou mais ativo foi o BiOI cuja síntese continha PVP e etilenoglicol (kap = 0,0207 min-1) e o BiVO4 foi o que apresentou a menor atividade (kap = 0,0013 min-1). Na degradação da prednisolona, a maior taxa de degradação foi obtida com 1 g L-1 de catalisador e no pH natural do fármaco, 6,8. Os ensaios de toxicidade revelaram que nem a prednisolona nem a mistura água e catalisador são tóxicas para as sementes de alface, as alíquotas provenientes da reação, porém, tiveram um aumento de sua toxicidade com o aumento do tempo de reação. / In this work, solvo and hydrothermal methods were applied to synthesize three types of bismuth catalysts (Bi2WO6, BiOI and BiVO4) aiming to the apply it in heterogeneous photocatalysis under visible light. Were investigated the influences of reaction time, calcination, addition of poly (vinyl pyrrolidone) (PVP) and the solvent type during synthesis on their morphology, crystallinity, surface area and band gap. The catalysts were characterized by scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD) and nitrogen adsorption/desorption. To evaluate photocatalytic activity of the synthesized samples, experiments were carried out in a stirred batch reactor, with the catalyst in suspension and a LED lamp as a source of visible light. The test molecules chosen were the rhodamine B dye for determination of the samples with higher activity and subsequently the drug prednisolone, and then was studied the effect of catalyst concentration and initial pH of the reaction medium. Toxicity tests were also perfomed with organism Lactuca sativa – lettuce seeds, to the toxicity of pure prednisolone, water and BiOI catalyst mixture and aliquots from prednisolone degradation after different reaction times. As a result, the Bi2WO6 samples presented good crystallinity and morphological similarities despite having undergone different treatments. The BiOI catalysts presented a significant difference in morphology, microspheres to microplates, when changed the solvent, while the BiVO4 sample presented a parallelepiped shape. In the photocatalytic tests with rhodamine B, the catalyst with the highest activity was BiOI, containing PVP and ethylene glycol (kap = 0.0207 min-1) in its synthesis, and the BiVO4 was the catalyst with the lowest activity (kap = 0.0013 min-1). In the prednisolone degradation, the highest degradation rate was obtained with 1 g L-1 of catalyst and natural pH of the drug, 6.8. The toxicity tests showed that neither prednisolone nor water and catalyst mixture are toxic to lettuce seeds, aliquots from reaction, however, had an increase in their toxicity with increasing reaction time.

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Ce travail de thèse porte sur l'étude de nouveaux matériaux vitreux, dopés par des ions bismuth ou des nanoparticules d’or, à destination de l’optique guidée. L’efficacité optique dans l’infrarouge des composants réalisés avec des verres dopés bismuth sont limitées par la méconnaissance du centre émetteur. Nous étudions ici les propriétés de luminescence d’un système plus simple : la silice pure. L’évolution des propriétés spectroscopiques, avec la température, d’une fibre optique micro-structurée à cœur de silice dopée bismuth est étudiée. Nous en déduisons les énergies de vibration du centre émetteur. L’influence de l’atmosphère de fabrication de préformes sur leurs propriétés spectroscopiques a ensuite été établie. Un procédé de fabrication de préformes par déposition chimique en phase vapeur (MCVD) est utilisé pour synthétiser des préformes sous atmosphères contrôlées. Les propriétés optiques de ces préformes et fibres optiques conventionnelles sont présentées. Ces résultats corroborent la présence dans la silice d’un centre émetteur dans l’infrarouge lié à une entité réduite du bismuth. Nous étudions alors les propriétés optiques linéaires et non-linéaires de verres massifs et de fibres optiques dopés par des nanoparticules d’or. Leur résonance plasmonique de surface est mise à profit pour fabriquer un verre dont le coefficient non-linéaire est supérieur à celui de la silice. Des monolithes de silice Sol-Gel dopée et densifiée à des températures basses sont utilisés pour la réalisation de fibres optiques micro-structurées. Nous observons un comportement d’absorbant saturable pour le verre massif alors que la fibre optique présente un comportement de limitation optique. / This thesis concerns the properties of two chemical elements which are bismuth ion and gold nanoparticles, for silica doped optical fiber. Efficiency device set up with bismuth doped silica fibers are limited by the misunderstanding of the infrared luminescent center. To this aim, we decided to use the stack and draw process to realize a microstructured optical fiber with a silica core doped only with bismuth. Evolution of spectroscopic properties of the optical fiber versus temperature is reported. We employed a model to deduce vibrational energies of the luminescent center. In a second time, we studied influence of the manufacturing atmosphere of Bismuth doped optical preforms on their spectroscopic properties. A chemical vapor deposition is use with more or less atmosphere during collapse step. Spectroscopic properties of bismuth doped silica preform are presented and discussed. All these results seem to confirm the presence in bismuth doped silica glass of a low valence state or a reduce species of the bismuth element. The second study concerns the linear and nonlinear properties of gold nanoparticles doped bulk glasses and optical fibers. In this work, we propose to start from monolithic silica xerogel with controlled porosity. It is then possible to obtain gold nanoparticles-doped glasses that can be used for the realization of micro-structured fibers using the Stack and Draw technique. Linear and nonlinear properties of bulk glass and optical fibers are studied. We will also present the properties the bulk glass that behaves like a saturable absorber and the optical fiber which presents optical limitation.