Wong Man Yung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 106-120). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of Contents --- p.vi / List of Figures --- p.xi / List of Plates --- p.xiii / List of Tables --- p.xv / Abbreviations --- p.xvi / Equations --- p.xviii / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Water disinfection --- p.1 / Chapter 1.2 --- Bacterial species --- p.2 / Chapter 1.2.1 --- Staphylococcus saprophyticus --- p.2 / Chapter 1.2.2 --- Enterobacter cloacae --- p.3 / Chapter 1.3 --- Disinfection methods --- p.4 / Chapter 1.3.1 --- Physical methods --- p.4 / Chapter 1.3.1.1 --- UV-C irradiation --- p.4 / Chapter 1.3.1.2 --- Solar disinfection --- p.5 / Chapter 1.3.2 --- Chemical methods --- p.6 / Chapter 1.3.2.1 --- Chlorination --- p.6 / Chapter 1.3.2.2 --- Ozonation --- p.7 / Chapter 1.3.2.3 --- Mixed disinfectants --- p.8 / Chapter 1.3.3 --- Other disinfection methods --- p.8 / Chapter 1.4 --- Advanced oxidation processes (AOPs) --- p.9 / Chapter 1.5 --- Photocatalytic oxidation (PCO) --- p.10 / Chapter 1.5.1 --- PCO process --- p.12 / Chapter 1.5.2 --- Photocatalysts --- p.14 / Chapter 1.5.2.1 --- Titanium dioxide (P25) --- p.15 / Chapter 1.5.2.2 --- Silver sensitized P25 (Ag/P25) --- p.16 / Chapter 1.5.2.3 --- Silicon dioxide doped titanium dioxide (SiO2-TiO2) --- p.17 / Chapter 1.5.2.4 --- Copper(I) oxide sensitized P25 (Cu2O/P25) --- p.18 / Chapter 1.5.3 --- Irradiation sources --- p.19 / Chapter 1.5.4 --- PCO disinfection mechanisms --- p.20 / Chapter 1.6 --- Bacterial defense mechanisms against oxidative stress --- p.22 / Chapter 2. --- Objectives --- p.25 / Chapter 3. --- Materials and Methods --- p.26 / Chapter 3.1 --- Chemicals --- p.26 / Chapter 3.2 --- Bacterial culture --- p.26 / Chapter 3.3 --- Photocatalytic reactor --- p.27 / Chapter 3.4 --- PCO efficacy test --- p.30 / Chapter 3.5 --- Optimization of PCO conditions --- p.31 / Chapter 3.5.1 --- Effect of P25 concentrations --- p.31 / Chapter 3.5.2 --- Effect of UV intensities --- p.32 / Chapter 3.5.3 --- Combinational study of P25 concentrations and UV intensities --- p.32 / Chapter 3.5.4 --- Effect of stirring rates --- p.32 / Chapter 3.5.5 --- Effect of initial cell concentrations --- p.33 / Chapter 3.6 --- PCO disinfection using different photocatalysts --- p.33 / Chapter 3.6.1 --- Effect of CU2O/P25 concentrations --- p.33 / Chapter 3.6.2 --- Effect of CU2O powder on the two bacterial species --- p.33 / Chapter 3.7 --- Transmission electron microscopy (TEM) --- p.34 / Chapter 3.8 --- Catalase (CAT) test --- p.37 / Chapter 3.9 --- Superoxide dismutase (SOD) activity assay --- p.39 / Chapter 4. --- Results --- p.40 / Chapter 4.1 --- Efficacy test --- p.40 / Chapter 4.2 --- PCO disinfection under UV irradiation --- p.40 / Chapter 4.2.1 --- Control experiments --- p.40 / Chapter 4.2.2 --- Optimization of PCO conditions using P25 as a photocatalyst --- p.42 / Chapter 4.2.2.1 --- Effect of P25 concentrations --- p.42 / Chapter 4.2.2.2 --- Effect of UV intensities --- p.45 / Chapter 4.2.2.3 --- Combinational study of P25 concentrations and UV intensities --- p.48 / Chapter 4.2.2.4 --- Effect of stirring rates --- p.54 / Chapter 4.2.2.5 --- Effect of initial cell concentrations --- p.57 / Chapter 4.2.3 --- Comparison of PCO inactivation efficiency between S. saprophyticus and E. cloacae --- p.60 / Chapter 4.2.4 --- PCO disinfection using different photocatalysts --- p.62 / Chapter 4.2.4.1 --- Control experiments --- p.62 / Chapter 4.2.4.2 --- Ag/P25 --- p.62 / Chapter 4.2.4.3 --- SiO2-TiO2 --- p.64 / Chapter 4.2.4.4 --- Cu2O/P25 --- p.64 / Chapter 4.3 --- PCO disinfection under visible light irradiation --- p.66 / Chapter 4.3.1 --- Effect of Cu2O/P25 concentrations --- p.67 / Chapter 4.3.2 --- Effect of CU2O powder on the two bacterial species --- p.70 / Chapter 4.4 --- Feasibility use of indoor light (fluorescent lamps) for PCO disinfection --- p.71 / Chapter 4.5 --- Transmission electron microscopy (TEM) --- p.74 / Chapter 4.5.1 --- Morphological changes induced by PCO using P25 as a photocatalyst --- p.74 / Chapter 4.5.2 --- Morphological changes induced by PCO using Cu2O/P25 as a photocatalyst --- p.77 / Chapter 4.6 --- Catalase (CAT) test --- p.80 / Chapter 4.7 --- Superoxide dismutase (SOD) activity assay --- p.82 / Chapter 5. --- Discussion --- p.83 / Chapter 5.1 --- Efficacy test --- p.83 / Chapter 5.2 --- PCO disinfection under UV irradiation --- p.83 / Chapter 5.2.1 --- Optimization study --- p.84 / Chapter 5.2.1.1 --- Effect of P25 concentrations --- p.84 / Chapter 5.2.1.2 --- Effect of UV intensities --- p.85 / Chapter 5.2.1.3 --- Combinational study of P25 concentrations and UV intensities --- p.86 / Chapter 5.2.1.4 --- Effect of stirring rates --- p.86 / Chapter 5.2.1.5 --- Effect of initial cell concentrations --- p.87 / Chapter 5.2.2 --- Comparison of PCO inactivation efficiency between S. saprophyticus and E. cloacae --- p.88 / Chapter 5.2.3 --- PCO disinfection using different photocatalysts --- p.89 / Chapter 5.2.3.1 --- Ag/P25 --- p.89 / Chapter 5.2.3.2 --- SiO2-TiO2 and Cu2O/P25 --- p.90 / Chapter 5.3 --- PCO disinfection under visible light irradiation --- p.90 / Chapter 5.3.1 --- Effect of Cu20/P25 concentrations --- p.91 / Chapter 5.3.2 --- Effect of CU2O powder on the two bacterial species --- p.92 / Chapter 5.4 --- Feasibility use of fluorescent lamps for PCO disinfection --- p.93 / Chapter 5.5 --- Transmission electron microscopy (TEM) --- p.95 / Chapter 5.5.1 --- Morphological changes induced by PCO using P25 as a photocatalyst --- p.95 / Chapter 5.5.2 --- Morphological changes induced by PCO using CU2O/P25 as a photocatalyst --- p.96 / Chapter 5.6 --- Catalase (CAT) test --- p.98 / Chapter 5.7 --- Superoxide dismutase (SOD) activity assay --- p.99 / Chapter 6. --- Conclusion --- p.101 / Chapter 7. --- References --- p.106 / Chapter 8. --- Appendix --- p.121

Made available in DSpace on 2017-07-21T20:43:46Z (GMT). No. of bitstreams: 1 Sabrina Marinho Kaplun.pdf: 2639962 bytes, checksum: a9f7e8225e77abb24e8a18b7dd472300 (MD5) Previous issue date: 2015-04-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The purpose of this study was to obtain, characterize and evaluate the photocatalytic activity of the surface modified titanium dioxide in relation to the unmodified titanium dioxide. Titanium dioxide (TiO2) anatase (commercial) was introduced into an oven made, with the function of modifying the external surface of the oxide by the effect of pressure, temperature and time. The modified titanium (TM) oxides and unmodified (TN) were characterized by the techniques of X-ray diffraction (XRD)and refinement by the Rietveld method, transmission electron microscopy (TEM) and determination of specific surface area. In heterogeneous photodegradation tests, degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was accompanied by UV/vis, high performance liquid chromatography efficiency (HPLC) and determination of total organic carbon (TOC). The influence of pressure on the surface of titanium dioxide resulted in a change in the external surface of titanium dioxide, surface irregularities increases, without changes in unit cell parameters and increases the surface area. The photocatalytic activity of the modified titanium dioxide (TM) was higher to the unmodified titanium dioxide (TN).The modified titanium dioxide had a higher percentage of degradation of the herbicide 2,4-dichlorophenoxyacetic acid and a higher mineralization making it more efficient. / A proposta desse trabalho consistiu em obter, caracterizar e avaliar a atividade fotocatalítica do dióxido de titânio modificado superficialmente em relação ao dióxido de titânio não modificado. O dióxido de titânio (TiO2) anatase (comercial) foi introduzido em um forno confeccionado, com a finalidade de modificar a superfície externa do óxido de titânio pelo efeito da pressão, temperatura e tempo. Os óxidos de titânio modificados (TM) e não modificados (TN) foram caracterizados pelas técnicas de difração de raios X (DRX) e refinamento pelo método de Rietveld, microscopia eletrônica de transmissão (MET) e determinação da área superficial específica. Nos ensaios de fotodegradação heterogênea, a degradação do herbicida 2,4-diclorofenoxiacético (2,4-D) foi acompanhada pelas técnicas de UV/vis, cromatografia líquida de alta eficiência (HPLC) e determinação de carbono orgânico total (COT). A influência da pressão na superfície do dióxido de titânio resultou em uma modificação na superfície externa do dióxido de titânio aumentando irregularidades na superfície, sem alterações nos parâmetros da célula unitária e com elevação da área superficial. A atividade fotocatalítica do dióxido de titânio modificado (TM) foi superior ao dióxido de titânio não modificado (TN). O dióxido de titânio modificado apresentou maior porcentagem de degradação do herbicida 2,4-diclorofenoxacético e uma maior mineralização o que o torna mais eficiente.

Propõe-se, pela primeira vez, a associação do tratamento fotocatalítico de amostra, direcionado à degradação e/ou eliminação de interferentes orgânicos, com a separação analito/matriz via geração de hidretos voláteis seguida de determinação por espectrometria de absorção atômica (HG-AAS). O fotocatalisador TiO2 (P-25) foi utilizado sempre em suspensão na amostra, e como fonte de radiação UV empregou-se lâmpada de mercúrio. Duas geometrias de reator fotocatalítico foram examinadas: irradiação estacionária de amostras contidas em cubetas de quartzo (3,5 mL); e irradiação em reator tubular constituído de bobina de Teflon montada em torno da lâmpada. Para avaliar a eficiência do tratamento sob diferentes condições, utilizou-se inicialmente o sistema-modelo Cd(II)-EDTA, com detecção do Cd(II) não quelado por voltametria de pulso diferencial em eletrodo de gota pendente de mercúrio, sabidamente não influenciada pelo TiO2 em suspensão. Nos estudos com HG-AAS, focalizou-se a aplicação do tratamento fotocatalítico à decomposição da arsenobetaína (Asb), um composto modelo interessante por ser refratário aos tratamentos convencionais (micro-ondas + digestão ácida). As condições selecionadas para a etapa de HG-AAS foram: concentração de HCl, 3 mol.L-1, concentração de NaBH4, 1% m/v em NaOH 0,1 mol.L-1, volume de amostra, 0,10 mL e temperatura do atomizador de tubo de quartzo, 980 °C. Nessas condições, as curvas de calibração obtidas por HG-AAS para As(III) e As(V) na faixa de 0,020 a 0,100 mg.L-1 (20 a 100 ppb) apresentaram linearidade e sensibilidade próximas, indicando eficiência de formação similares, característica esta favorável à quantificação total de arsênio em aplicações futuras a amostra reais. Estudos preliminares mostraram que a taxa de recuperação do arsênio é maior no tratamento fotocatalítico realizado em meio alcalino, (pH=12) em razão da menor tendência à adsorção de arsênio em TiO2 nesse meio frente ao neutro e ácido. Parâmetros como o tempo de irradiação, concentração do fotocatalisador e de Asb, além da influência de O2 molecular como scavenger de elétrons também foram investigados. Nas condições selecionadas, partindo-se de uma solução de Asb 0,075 mg.L-1 em arsênio, alcançou-se recuperação aproximada de 80% mediante irradiação por 15 minutos e de 100% após 45 minutos. A decomposição da Asb pelo método fotocatalítico proposto foi confirmada por espectrometria de massa com ionização por electrospray e estudos adicionais poderão revelar se as espécies de arsênio envolvidas na geração da arsina encontram-se completamente mineralizadas. / The combination of photocatalytic sample preparation, aiming degradation of organic interferences, with analyte/matrix separation by generation of volatile hydrides followed by atomic absorption spectrometric determination (HG-AAS) is proposed for the first time in this work, mainly devoted to the investigation of total arsenic analysis. A mercury lamp served as source of UV-radiation and the photocatalyst, TiO2 (P25), was used as a suspension in the sample solution. Two geometries of photocatalytic reactor were examined: stationary irradiation of a set of samples contained in 3.5 mL quartz cuvettes (preferred one for the present application) and stopped-flow irradiation of a sample in a tubular reactor consisting of a Teflon tube coiled around the lamp. Evaluation of the digestion efficiency of the reactors under different conditions was made with help of the model system Cd(II)-EDTA, with detection of the unchelated Cd(II) by differential pulse voltammetry with the hanging mercury drop electrode, known to work in the presence of TiO2 suspension. The subsequent studies in combination with HG-AAS focused on the photocatalytic degradation of arsenobetaine (Asb), chosen as a model because it is particularly resistant to conventional treatments (microwave + acid digestion). The following conditions were established for the HG-AAS step: HCl concentration (3 mol.L-1) and NaBH4 concentration (1% m/v in NaOH 0,1 mol.L-1), sample volume (0.10 mL) and atomization temperature (980 °C). Calibration curves for As (III) and As (V) by HG-AAS in the range of 0,020 to 0,100 mg.L-1 (20 a 100 ppb) conveyed in slope and linearity, indicating the same efficiency of arsine formation from both species, favoring the total quantification of arsenic in the sample. Alkaline medium (pH=12) was preferred for the photocatalytic digestion because recoveries of arsenic were better than in neutral or acidic medium, possibly due to lower losses by adsorption of arsenic species on TiO2. The effects of parameters such as irradiation time, concentration of the photocatalyst and of arsenobetaine, as well as the influence of molecular O2 as an electron scavenger were investigated. Under selected conditions and for a starting solution of 0,075 mg.L-1 Asb an arsenic recovery of 80% approximately was obtained after 15 minutes of irradiation while full recovery required 45 minutes. The decomposition of the Asb molecule after irradiation was confirmed by electrospray mass spectrometry and a further study may reveal if the arsenic species involved in the arsine generation are fully mineralized ones.

Nature uses sunlight either as energy source or as information carrier. Photoreception is achieved by two groups of specialised proteins: photo-enzymes that catalyse photoreactions and photosensors that initiate physiological functions. In the present work mechanistic studies were conducted on one representative of each group by using site-directed mutagenesis as well as stationary and time-resolved spectroscopy. The photo-enzyme NADPH:Protochlorophyllide Oxidoreductase (POR) catalyses the light-dependent C17-C18 double bond reduction of protochlorophyllide, including a hydride and a proton transfer, to produce chlorophyllide, the immediate precursor of chlorophyll. POR provides a unique opportunity to study the hydride transfer mechanism in detail. Three distinct intermediates, prior to product formation, were observed that were interpreted as electron and proton-coupled electron transfer reactions from NADPH indicating a sequential hydride transfer mechanism. An active-site mutant, POR-C226S, yields distinct different intermediates compared to POR wild type but ends in the same chlorophyllide stereoisomer most likely due to an altered protochlorophyllide binding. This work provides the first direct observation of a stepwise hydride transfer mechanism in a biological system. Cryptochromes (CRY) are so far defined as flavoprotein blue-light photosensors that regulate the circadian clock throughout nature and are suggested as the candidate magnetoreceptor in animals. Animal CRY are subdivided into two classes of proteins: the light-responsive Type I (invertebrates) and the light-independent Type II (mainly vertebrates). The molecular basis of their different roles in the circadian clock is still unknown. Animal Type I CRY are suggested to undergo conformational changes - required for induction of subsequent signalling cascades - induced by the change in the FAD redox state due to light absorption. The study shows that in contrast to Type I animal Type II CRY do not bind tightly FAD as a cofactor due to the lack of structural features and therefore provide the molecular basis for their different biological roles ruling out a direct photomagnetoreceptor function. Further, detailed studies on a fruit fly (Dm)CRY reveal that it does not undergo a photocycle as FAD release and Trp decomposition were observed. Thus, it is suggested that light is a negative regulator of DmCRY stability linking the initial photochemistry to subsequent dark processes leading to signal transduction on a molecular level.

Des films multicouches à base de nanoparticules de TiO2 et d’Ag ont été construits sur des substrats modèles et des textiles via la technique du Layer-by-Layer (LbL). Les films à base de nanoparticules de TiO2 construits sur substrats modèles ont montré un comportement photocatalytique non conventionnel pour la minéralisation de l’acide formique en phase gaz sous irradiation UV-A, et une minéralisation très importante a été obtenue avec un film possédant une unique couche de nanoparticule de TiO2. Ces films ont également montré des propriétés biocides sous irradiation UV-A. La mise en œuvre d’une méthode one-pot, combinant la synthèse photo-induite des nanoparticules d’Ag et dépôt de la couche de TiO2 par LbL, a permis la synthèse de nanoparticules d’Ag directement au sein des films et une exaltation très importante des propriétés photocatalytiques des films. Les méthodes de constructions ont été transférées avec succès sur textiles. Les films restent photocatalytiquement actifs et biocides sous irradiation UV-A après plusieurs cycles de lavages. / TiO2 and Ag nanoparticle multilayered films were constructed on model substrates and textiles via Layer-by-Layer (LbL) assembly. The TiO2 nanoparticle based films constructed on model substrates showed a non-conventional photocatalytic behaviour for gas phase formic acid mineralisation upon UV-A irradiation, and a high mineralisation was obtained for a single layer TiO2 nanoparticle film. These films also showed biocidal properties upon UV-A irradiation. The elaboration of a one-pot method, combining the photo-induced synthesis of Ag nanoparticles and the LbL deposition of TiO2 nanoparticle layer, allowed the direct synthesis of Ag nanoparticles within the films and a high enhancement of the film photocatalytic properties. The construction methods were successfully transfered on textile surfaces. The films were photocatalytically active and biocidal under UV-A irradiation after several washing treatment cycles.

O aumento da concentração de gases de efeito estufa (GEE) de fontes antropogênicas tem sido visto como uma das principais contribuições para o aquecimento global, ameaçando a vida no planeta. O dióxido de carbono (CO2) é um dos principais GEE e suas fontes geradoras estão relacionadas a processos essenciais à sociedade, como a produção de energia, produtos diversos e transporte. A conversão do CO2 parece ser uma alternativa promissora para reduzir a emissão deste gás na atmosfera. De particular interesse para este estudo, a fotorredução do CO2 a metanol pode contribuir para mitigar o problema dos GEE, gerando um importante insumo da indústria química. Assim, este estudo tem por objetivo utilizar cálculos quanto-mecânicos, como a Teoria do Funcional Densidade, para investigar um caminho para a reação de redução do CO2. A reação de redução do CO2 à ácido fórmico, formaldeído e metanol foi estudada sem a interação com o catalisador e na presença de dióxido de titânio como catalisador. Foi realizada uma comparação de cálculos em diferentes níveis teóricos e diferentes bases, com dados experimentais. Para os cálculos envolvendo o TiO2, foi utilizado o nível B3LYP/6-31G(d,p). Frequências vibracionais também foram calculadas para cada etapa, permitindo a identificação de possíveis estados de transição e estimativa de barreiras de reação (energia potencial). Cálculos de coordenada intrínseca de reação (IRC) foram empregados para confirmar que os estados de transição encontrados, estão relacionados a cada etapa estudada. A comparação da redução do dióxido de carbono a ácido fórmico, com e sem catalisador, mostrou que a presença do dióxido de titânio reduziu em mais de 25,0% a barreira reacional desta etapa

Ces dernières années, les énormes progrès réalisés en nanotechnologie ainsi qu’en science des matériaux ont conduit à la préparation de nombreuses nouvelles nanoparticules sans réellement connaître l’ensemble des propriétés associées à leurs dimensions. La première partie de notre travail vise à évaluer les risques et les problèmes associés aux nanomatériaux, en termes de toxicité, en utilisant des nanoparticules de ZnO. Nous avons tout d’abord étudié la capacité de ces nanoparticules à générer des espèces réactives d’oxygènes (EROs) sous irradiation UV en utilisant trois types des quantum dots (QDs) comme modèles, ZnO, ZnO dopé avec des ions Cu2+ et ZnO avec des ions Cu2+ adsorbés à sa surface. Les trois types des QDs ont montré une forte capacité à générer des EROs mais ceux modifiés par les ions Cu2+ en périphérie sont les plus producteurs. Ces QDs inhibent également le plus fortement la croissance de la bactérie E. coli. La toxicité n’est cependant pas dépendante des EROs photo-produits ni du zinc (+2) libéré par les QDs et montre qu’un mécanisme plus complexe doit être considéré. Dans une second partie, nous avons tenté d’améliorer l’activité photocatalytique de nanobâtonnets de ZnO en les associant à de l’oxyde de graphène réduit (rGO). Des nanocomposites ZnO/rGO ont été préparés par voie solvothermale et utilisés pour la phototodégradation du colorant Orange II comme modèle de polluant. Les résultats obtenus montrent que le photocatalyseur ZnO/rGO est très efficace sous irradiation solaire ou visible et qu’il est peu sensible à des variations de pH ou à la présence de perturbateurs dans le milieu. Finalement, le photocatalyseur est très stable et peut être réutilisé plus de dix fois sans perte notable d’activité. / In recent years, tremendous advances in nanotechnology and materials science have led to the synthesis of many new nanoparticles without really knowing all the properties associated with their dimensions. The first part of our work aims to evaluate the risks and problems associated with nanomaterials, in terms of toxicity, using ZnO nanoparticles. We first studied the ability of these nanoparticles to produce reactive oxygen species (ROS) under UV irradiation using three ZnO-based quantum dots (QDs) as models, ZnO, ZnO doped with Cu2+ ions and ZnO with chimisorbed Cu2+ ions at their periphery. The three QDs have a strong capacity of generating ROS but those modified with Cu2+ at their surface were found the be the highest producers. These dots were also found to inhibit more markedly the growth of the E. coli bacteria. The toxicity does neither depend on the amount of photo-generated ROS nor on the amount of Zn(+2) leaked by the QDs, thus indicating that a more complex mechanism should be considered. In a second part, we tried to improve the photocatalytic efficiency of ZnO nanorods by associating these nanomaterials with reduced graphene oxide (rGO). ZnO/rGO composites were prepared by a solvothermal method and applied for the photodegradation of Orange II used as model pollutant. Results obtained demonstrate that the ZnO/rGO photocatalyst is highly efficient under solar and under visible light irradiation and weakly sensitive to pH changes and to the presence of perturbators in the reaction medium. Finally, the photocatalyst is stable and can be reused up to ten times without significant loss of catalytic activity.

Made available in DSpace on 2015-09-25T12:23:36Z (GMT). No. of bitstreams: 1 SALOMAO_DE_ANDRADE_PASCOAL.pdf: 1571379 bytes, checksum: 8dcb3d302822615da27bf933016a3cef (MD5) Previous issue date: 2006-02-23 / The industry is a section of the contemporary society with great pollutant potential of the environment, especially of the aquatic ecosystems. The tanning industries are big producing of dejections with significant amounts of organic matter and of chrome. The conventional processes of treatment applied those dejections, not always they possess good effectiveness. Actuality, the Advanced Oxidation Processes represent an excellent alternative of tertiary treatment. In the present study, the application of the heterogeneous photocatalysis was evaluated, being used a photocatalyst (TiO2) immobilized, in the tertiary treatment of synthetic liquid effluents representative of tanning industries. It was aimed at to remove Cr(VI) and organic matter. The photocatalytic reactor was of the type Fixed Bed of Fine Film, built with a plate of glass arrayed for the fixation of TiO2. It was adopted as radiation sources, the sun and lamps issuing of UV radiation (l= 250 nm). The smallest values of removal effectiveness for Cr(VI) they were of 62% and 51% and of DOC they were from 60% and 53% to the experiments done with radiation UV originating from of the sun and of lamps, respectively. The results of the parameters related to the reduction phases and oxidation of the heterogeneous photocatalysis, they showed that the exhibition in the sun, he/she has effectiveness of larger relative removal than the exhibition to UV lamps. The data of relative removal of Cr(VI) and of DOC and the constants kinetics of these parameters, they indicated that the adopted experimental configurations optimized the phase of reduction of the heterogeneous photocatalysis. / A indústria é um setor da sociedade contemporânea com grande potencial poluidor do meio ambiente, especialmente dos ecossistemas aquáticos. As indústrias de curtume são grandes produtoras de dejetos com significativas quantidades de material orgânico e de cromo. Os processos convencionais de tratamento aplicados a esses dejetos, nem sempre possuem boa eficácia. Atualmente, os Processos Oxidativos Avançados representam uma excelente alternativa de tratamento terciário. No presente estudo, avaliou-se a aplicação da fotocatálise heterogênea, usando-se um fotocatalisador (TiO2) imobilizado, no tratamento final de efluentes líquidos sintéticos representativos de indústrias de curtume. Objetivou-se remover Cr(VI) e matéria orgânica. O fotorreator foi do tipo Leito Fixo de Filme Fino, construído com uma placa de vidro jateado para a fixação do TiO2. Adotou-se como fontes de radiação, o sol e lâmpadas germicidas emissoras de radiação UV (l= 250 nm). Os menores valores de eficácia de remoção para Cr(VI) foram de 62% e 51% e de DQO foram de 60% e 53% para os experimentos feitos com radiação UV oriundas do sol e de lâmpadas, respectivamente. Os resultados dos parâmetros relacionados às fases de redução e oxidação da fotocatálise heterogênea, mostraram que a exposição ao sol, tem eficácia de remoção relativa maior do que a exposição à lâmpadas UV. Os dados de remoção relativa de Cr(VI) e de DQO e as constantes cinéticas destes parâmetros, indicaram que as configurações experimentais adotadas otimizaram a fase de redução da fotocatálise heterogênea.

Submitted by Cláudia Bueno (claudiamoura18@gmail.com) on 2016-03-03T14:57:43Z No. of bitstreams: 2 Dissertação - Bruna Guimarães Isecke - 2015.pdf: 1944574 bytes, checksum: 66e445d4335fe545fd67e110898abe01 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-03-03T15:34:17Z (GMT) No. of bitstreams: 2 Dissertação - Bruna Guimarães Isecke - 2015.pdf: 1944574 bytes, checksum: 66e445d4335fe545fd67e110898abe01 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2016-03-03T15:34:17Z (GMT). No. of bitstreams: 2 Dissertação - Bruna Guimarães Isecke - 2015.pdf: 1944574 bytes, checksum: 66e445d4335fe545fd67e110898abe01 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2015-04-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Several studies point to the presence of emerging pollutants in surface water, groundwater and public water supply in many countries. Such substances are not covered by legislation and derived from effluent discharges with inadequate or no treatment. In this context, fall within the synthetic estrogens as EE2 (ethinylestradiol) that are found in the residual medium in the environment, which can have adverse effects on aquatic organisms as well as for terrestrial organisms. These hormones are absorbed by the body, suffer metabolic reactions and a quantity of them, both in its form as unmetabolised in metabolized form, it is excreted to the environment. As these substances are not easily biodegradable and have harmful pharmacological properties when used incorrectly, through contaminated water, there is growing concern about its destination, especially when taking into account the environmental risk assessment. For these reasons, the detection, elimination and investigation of the fate of these estrogens has become priority on environmental chemistry. These products are found in low concentrations (μg.L-1 and ng.L-1), but even so, can be harmful to organisms through bioaccumulation. There are still few ecotoxicological studies related to the exposure of organisms to substances considered endocrine disruptors. The aim of the study was to develop and validate an analytical method for high-performance liquid chromatography (HPLC) to identify and quantify ethinyl estradiol, the study of degradation of the same compound in a photocatalytic reactor and also the calculation of the reaction kinetics for each curve ethinyl estradiol degradation. For analytical validation experiments were performed as set forth in the RE 899 2003 ANVISA. For the degradation experiments were carried application of UV settling and also photocatalysis experiments using titanium dioxide (TiO2) in suspension. By applying a 22 factorial design pH parameters were studied and mass of the catalyst and also its interaction with regard to treatment efficiency. The reactor was operated in batch and in continuous flow, in both cases there optimization. The analytical method was effective for detection and quantification of ethinylestradiol. The photocatalytic degradation test batch procedure presented great efficiency degradation of ethinyl estradiol present in water, obtaining a mean degradation of about 99% in about 120 minutes. The factorial design has shown that the most relevant factor in relation to the degradation efficiency was the pH, although there has been the appearance of a degradation by-product when used a basic pH (8.0). A greater treatment efficiency with smaller mass of TiO2 (0.05 gL-1). The reaction order and constant speed found for the experiments were as between 1 and 2. When the system is operating in continuous flow ethinyl estradiol degradation was approximately about 84% after optimization. The study shows that photocatalysis is very efficient to ethinyl estradiol degradation in water. / Vários estudos realizados apontam a presença de poluentes emergentes em águas superficiais, subterrâneas e de abastecimento público em vários países do mundo. Tais substâncias não são contempladas pela legislação e derivam de lançamentos de efluentes com tratamento inadequado ou inexistente. Nesse contexto, inserem-se os estrogênios sintéticos como o EE2 (etinilestradiol) que são encontrados em forma residual no meio ambiente, o que pode acarretar efeitos adversos tanto em organismos aquáticos quanto em organismos terrestres. Esses hormônios são absorvidos pelo organismo, sofrem reações metabólicas e uma quantidade deles, tanto em sua forma não metabolizada quanto em forma metabolizada, é excretada ao meio ambiente. Como essas substâncias não são facilmente biodegradáveis e possuem propriedades farmacológicas danosas quando utilizadas de forma incorreta, através de águas contaminadas, é crescente a preocupação em relação à sua destinação, principalmente ao se levar em consideração a avaliação de risco ambiental. Por tais motivos, a detecção, a eliminação e investigação do destino desses estrogênios tem se tornado prioridade em relação à química ambiental. Estes produtos são encontrados em baixas concentrações (μg.L-1 e ng.L-1) mas, mesmo assim, podem ser danosos aos organismos por meio de bioacumulação. Ainda existem poucos estudos ecotoxicológicos relacionados à exposição de organismos a substâncias consideradas desreguladoras do sistema endócrino. O objetivo do estudo foi desenvolver e validar um método analítico em cromatografia líquida de alta eficiência (CLAE) para identificação e quantificação de etinilestradiol, o estudo de degradação do mesmo composto em um reator fotocatalítico e também o cálculo da cinética de reação para cada curva de degradação de etinilestradiol. Para a validação analítica foram realizados experimentos conforme estabelecidos na RE 899 de 2003 da ANVISA. Para os experimentos de degradação foram realizados aplicação de radicação UV e também experimentos de fotocatálise com a utilização de dióxido de titânio (TiO2) em suspensão. Através da aplicação de um planejamento fatorial 22 foram estudados os parâmetros pH e massa do catalisador e também sua interação em relação a eficiência de tratamento. O reator foi operado em batelada e em fluxo contínuo, em ambos os casos houve a otimização. O método analítico se mostrou eficiente para detecção e quantificação de etinilestradiol. Os ensaios de degradação fotocatalítica em regime de batelada apresentaram grande eficiência na degradação do etinilestradiol presente em água, obtendo-se degradação média de cerca de 99% em aproximadamente 120 minutos. O planejamento fatorial nos mostrou que o fator mais relevante em relação à eficiência de degradação foi o pH, embora, tenha havido a aparição de um subproduto de degradação quando se utilizou um pH básico (8,0). Houve maior eficiência de tratamento com menor massa de TiO2 (0,05 g.L-1). A ordem de reação e constantes de velocidades encontradas para os experimentos foram de ordem entre 1 e 2. Quando o sistema foi operando em fluxo contínuo houve degradação de etinilestradiol em cerca de aproximadamente 84%, após sua otimização. O estudo nos mostrou que a fotocatálise é bastante eficiente para a degradação de etinilestradiol em água.

Neste trabalho focou-se na preparação de materiais com aplicação em processos de tratamento de compostos orgânicos poluentes. Especificamente, buscou-se correlacionar as propriedades físicas e químicas dos materiais com as suas respostas catalíticas nos processos de fotocatálise heterogênea e de ozonização. Empregando-se o método de precipitação, preparou-se óxidos mistos de TiO2 e CeO2 em diferentes proporções. A caracterização destes materiais mostrou uma correlação entre a formação de partículas anisotrópicas, com morfologia do tipo bastão, e a capacidade de degradação de fenol pelo processo de fotocatálise heterogênea. Em particular, obteve-se 70% de degradação de fenol para o material com 20% CeO2. A interação entre o TiO2 e CeO2 também foi estudada em materiais preparados pelo método sol-gel. A presença do CeO2 retardou a transformação do polimorfo anatásio para rutilo, bem como manteve a estrutura de poros quando os matareriais foram calcinados a 650 ºC. Esta maior estabilidade possui relação com as propriedades fotocatalíticas dos materiais calcinados. Degradou-se 77% de fenol com o fotocatalisador 0,5% CeO2. Fotocatalisadores híbridos de SiMgOx e TiO2 foram preparados pela deposição de diferentes quantidades de TiO2 em placas de sepiolitas por slip-casting. Avaliou-se os materiais híbridos na degradação de ar contaminado com tricloroetileno (TCE) pelo processo de fotocatálise heterogênea. Observou-se uma dependência entre a espessura da camada de TiO2 e a taxa de degradação e mineralização do TCE, obtendo-se até 100% de degradação do TCE. Os materiais híbridos também tiveram suas propriedades catalíticas avaliadas na fotodegradação de TCE utilizando radiação solar. A combinação das propriedades de adsorção da sepiolita e fotocatalíticas do TiO2 possibilitaram 100% de degradação do TCE via incidência de radiação solar. O estudo de materiais híbridos também foi realizado com a preparação de esferas híbridas de carbono e CeO2. Este novo material foi preparado em uma única etapa, pelo método hidrotermal, sem a necessidade de emprego de solventes orgânicos. As esferas híbridas foram aplicadas na degradação de solução aquosa de ácido salicílico pelo processo de ozonização. As esferas eram, possívelmente, formadas por um core de carbono com nanopartículas de CeO2 dispersas em sua superfície hidrofílica. O efeito sinérgico entre a estrutura de carbono e o CeO2 resultou em um aumento de 25% na mineralização da solução de ácido salicílico pelo processo de ozonização. / This study was focused on the preparation of materials applied to the treatment of organic pollutant compounds. The main idea was to correlate the physical and chemical properties of these materials with their catalytic responses in heterogeneous photocatalysis and ozonation processes. Using the precipitation method, TiO2 and CeO2 mixed oxides were prepared in different proportions. The characterization of these materials showed a correlation between the formation of anisotropic rod-like particles and the capacity of degradation of phenol by a heterogeneous photocatalysis process. It was actived 70% of phenol degradation using the material with 20% CeO2. The interaction between TiO2 and CeO2 was also studied in materials prepared by the sol-gel method. The presence of CeO2 retarded the transition from anatase to rutile polymorphic, as well as maintained the porous structure when the materials were calcinated at 650 ºC. This major stability is related to the photocatalytic properties of the calcinated materials. For instance, 77% of the phenol was degraded using the 0.5% CeO2 photocatalyst. Hybrid photocatalysts composed by SiMgOx and TiO2 were prepared by depositing different amounts of TiO2 on sepiolite plates by slip-casting method. The performances of hybrid materials were evaluated by the degradation of contaminated air with trichloroethylene (TCE) using the heterogeneous photocatalysis process. A correlation between the thickness of the TiO2 layer and the degradation and mineralization rates of TCE was observed, obtaining up to 100% degradation of the TCE. Also, the catalytic properties of the hybrid materials were evaluated by TCE photodegration using solar radiation. A combination of the adsorption properites of the sepiolite and the photocatalytic properties of TiO2 allowed up to 100% of TCE degradation under incidence of solar radiation. The study of hybrid materials was also carried out with the preparation of carbon and CeO2 hybrid spheres. This novel material was prepared in one-pot step, using the hydrothermal method, without organic solvents. The hybrid spheres were used in the degradation of aqueous solution of salicylic acid by the ozonization process. The spheres were possibly formed by a core containing carbon with CeO2 nanoparticles dispersed on their hydrophilic surface.The synergetic effect between the carbon structure and the CeO2 resulted in an increase of 25% in the salicylic acid solution mineralization.