Heterogeneous nanostructures such as coaxial nanotubes, nanowires and nanorods have been of growing interest due to their potential for high energy-conversion efficiencies and charge/discharge rates in solar cell, energy storage and fuel cell applications. Their superior properties at nanoscale as well as their high surface area, fast charge transport along large interfacial contact areas, and short charge diffusion lengths have made them attractive components for next generation high efficiency energy-conversion devices. The primary focus of this work was to understand the doping mechanism of TiO2 nanotube exclusively with strontium as an alkaline earth metal to shine light on the relation between the observed enhancement in photocatalytic properties of doped TiO2 nanotubes and its structural and electronic characteristics. The mechanism of Sr incorporation into the TiO2 nanotube structure with the hypothesis of possibility of phase segregation has been explored in low concentrations as a dopant and in very high concentrations by processing of SrTiO3 nanotube arrays. Detailed experimental examination of the bulk and surface of the Sr-doped nanotubes has been performed to understand the effect of dopant on electronic structure and optical properties of the TiO2 nanotubes. Moreover, in order to minimize the polarizations associated with the ionic/electronic charge transport in the electrolyte and anode of solid oxide fuel cells (SOFCs), a new platform is developed using vertically oriented metal oxide nanotube arrays. This novel platform, which is made of coaxial oxide nanotubes on silicon substrates, has the potential to simultaneously lower the operating temperature and production cost leading to significant enhancement in the performance of micro-SOFCs.

Semiconductor photocatalysis has received considerable attention in recent years as an alternative for treating water polluted with hazardous organic chemicals. The process, as a means of removal of persistent water contaminants such as pesticides, which exhibit chemical stability and resistance to biodegradation, has attracted the attention of many researchers. To a lesser extent, it has also been studied for decontamination of water containing toxic metals. Precious and common metals enter waters through washing, rinsing, pickling and surface treatment procedures of industrial processes, such as hydrometallurgy, plating and photography. As a result we are living in an environment with a multitude of potentially harmful toxic metal ions. In contrast, the demand for metals increases significantly with the development and growth of industry. Even though research on the photocatalytic recovery of waste and noble metals has escalated in the past 10 years, the practical implementation of these processes is not yet justified. The successful implementation of large scale reactors, for industrial application, has to consider several reactor design parameters that must be optimised, such as reactor geometry and the utilization of radiated energy. In this study the effect of various parameters such as initial platinum(IV)chloride concentrations, initial sacrificial reducing agent (ethanol) concentrations, catalyst (TiO2) concentration, pH, temperature and light intensity has been investigated as a first step towards optimising a photocatalytic batch and photocatalytic flow reactor. Langmuir–Hinshelwood kinetics has been applied to calculate the photocatalytic rate constant kr as well as the adsorption equilibrium constant Ke for both the initial platinum(IV) dependency as well as the initial ethanol concentration dependency. The results in this study may be used in future work for the optimisation and comparison of both batch and flow reactors towards the industrial implementation of these processes. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

L'analyse protéomique est une méthode de choix pour la recherche de biomarqueurs. Sans à priori, elle permet d'établir un catalogue de protéines qui sont exprimées dans une cellule, un tissu ou un organisme entier. Cette approche a été mise en œuvre pour une analyse protéomique de cellules coliques cancéreuses et une analyse phosphoprotéomique de biopsies hépatiques.L'étude de cellules coliques cancéreuses transformées par le gène cytosine désaminase et traitées par la prodrogue 5-fluorocytosine a été réalisée par électrophorèse bidimensionnelle des extraits protéiques. L'analyse d'image a permis la quantification de 353 protéines et isoformes dont 14 sont surexprimées et 4 sous exprimées lors d'un traitement par la prodrogue. Parmi les protéines dont l'expression est affectée par le traitement, l'HSP90 présente un niveau d'expression constant mais est identifiée sous deux formes qui diffèrent par leur pI. L'analyse par spectrométrie de masse à identifier une phosphorylation de ser 254 qui pourrait contribuer à la régression tumorale.Après avoir développé une méthode HPLC-TiO2 pour la purification de phosphopeptides, une analyse protéomique de 24 biopsies humaines provenant de carcinomes hépatocellulaires sur foie non fibreux (nf-CHC) et de tissus sains a été réalisée avec la technologie iTRAQ. Les peptides surexprimés dans les tumeurs correspondent à des protéines de choc thermiques, des protéines liées à l'ADN/ARN (histones, protéines du splicéosome), des protéines de la phase 1 de la détoxification (carboxyestérase, époxide hydrolase), les protéines du cytosquelette (actinine, tubuline), des protéines ou enzymes anti-oxydantes (superoxide dismutase, thiorédoxine). Les peptides sous-exprimés correspondent à des protéines du cycle de l'urée, de la détoxification (alcool déhydrogénase) du métabolisme des sucres, des lipides et des acides aminés. Dans la fraction TiO2, 19 phosphopeptides sont significativement surexprimés et 15 phosphopeptides sont significativement sous exprimés, mettant en en évidence une surreprésentation du motif -(S/T)P- parmi les phosphopeptides surexprimés dans les tumeurs. Une activation des proline directed kinases ou une inhibition des phosphatases correspondantes est donc probablement un événement caractéristique des nf-CHC. Ces peptides/protéines dérégulées sont autant de biomarqueurs potentiels pour le carcinome hépatocellulaire.

Semiconductor photocatalysis has received considerable attention in recent years as an alternative for treating water polluted with hazardous organic chemicals. The process, as a means of removal of persistent water contaminants such as pesticides, which exhibit chemical stability and resistance to biodegradation, has attracted the attention of many researchers. To a lesser extent, it has also been studied for decontamination of water containing toxic metals. Precious and common metals enter waters through washing, rinsing, pickling and surface treatment procedures of industrial processes, such as hydrometallurgy, plating and photography. As a result we are living in an environment with a multitude of potentially harmful toxic metal ions. In contrast, the demand for metals increases significantly with the development and growth of industry. Even though research on the photocatalytic recovery of waste and noble metals has escalated in the past 10 years, the practical implementation of these processes is not yet justified. The successful implementation of large scale reactors, for industrial application, has to consider several reactor design parameters that must be optimised, such as reactor geometry and the utilization of radiated energy. In this study the effect of various parameters such as initial platinum(IV)chloride concentrations, initial sacrificial reducing agent (ethanol) concentrations, catalyst (TiO2) concentration, pH, temperature and light intensity has been investigated as a first step towards optimising a photocatalytic batch and photocatalytic flow reactor. Langmuir–Hinshelwood kinetics has been applied to calculate the photocatalytic rate constant kr as well as the adsorption equilibrium constant Ke for both the initial platinum(IV) dependency as well as the initial ethanol concentration dependency. The results in this study may be used in future work for the optimisation and comparison of both batch and flow reactors towards the industrial implementation of these processes. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Titania-based photocatalysts have been extensively studied for the oxidative photodestruction of organic pollutants in wastewaters, releasing non-toxic substances such as CO2, HCl, and water. However, commercial exploitation of this process is limited by the fact that titania is only active under UV irradiation (wavelength below about 388 nm), which is only less than 5% of solar light energy. Sol-gel synthesised catalyst specimens were characterised to determine the correlation between preparation conditions on morphology (XRD, SEM), optical (bandgap energy level) and physicochemical properties (BET surface area, pore volume, acid site density, acid site strength and type) of the photocatalysts. These spesific properties would then be linked to their photoactivity using aqueous aliphatic and aromatic model pollutants. This study has demonstrated that sol-gel synthesised doped titania photocatalysts, especially Pt/TiO2, may be used to effectively degrade non-volatile acids (DL-malic acid, dichloroacetic acid, and p-hydroxybenzoic acid) under visible light and UV irradiation with significant photoactivity suitable for the solar light application of photocatalytic wastewater treatment. A significant drop in band-gap energy was found for all titania sol-gel catalysts doped with Pt, Co, and Ce with values between 1.41 to 1.78 eV. The BET areas of the photocatalysts were also higher (65-117 m2/g) than that of Degussa P25 (50 m2/g). The visible-light photomineralisation of the three pollutants with Pt-TiO2 specimen were further extended to evaluate the effects of major variables in a bubble-column photoreactor on the photodegradation activities. Those major variables were lamp intensity, oxygen concentration, initial pH, catalyst dosage, and inital pollutant concentration. All the three pollutants seemed to follow the Langmuir-Hinselwood model with dual adsorption sites which implicated a bimolecular surface rate-limiting step probably between the adsorbed organic substrate and a surface hydroxyl (or peroxy) radical. A study of the CeyCoxTi(1-x)O3+d perovskite was conducted to investigate the influence of metal composition and pH on the intrinsic optophysical attributes as well as p-hydroxybenzoic acid degradation under UV irradiation. The perovskite UV photoactivities were lower than that of pure TiO2 likely due to excessive loading (metal content) creating new oxide phases act as electron-hole recombination center, regardless better physicochemical attributes of some of the perovskite samples. The role of aging time and calcination temperature on the sol-gel synthesised TiO2 was also explored. Higher calcination temperature (from 250 to 700 0C) resulted in TiO2 photocatalysts with better crystallinity, which is important for OH group formation as active sites for photodegradation. Despite of some advantages from higher temperature preparation, some detrimental effects such as decreased acidity attributes, surface area, and pore volume were also observed. The significant red-shift of sol-gel synthesized TiO2 into visible light, especially for 250 0C specimen since 600 or 700 0C had extremely low activities, has promising implications that this specimen might be used for solar application to substitute Pt-doped TiO2 in order to produce a more cost effective photocatalyst. Aging period (1 to 14 days) did not have any discernible effect on the band-gap value and acid-site density. Even so, the highest acid site strength was obtained with an aging time of 10 days. From the overall perspective, aging time longer than 3 days did not bring noticeable benefits to both catalyst attributes and photoactivities.

No description available.

Submitted by Roberto de Aguiar Ramos Junior null (robeerto.aguiar.ramos@gmail.com) on 2018-04-03T14:25:40Z No. of bitstreams: 1 dissertaçao_final.pdf: 2202514 bytes, checksum: b29c60407d282d9848bdfc887c1a97c8 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-04-04T19:31:40Z (GMT) No. of bitstreams: 1 ramosjunior_ra_me_bauru.pdf: 2202514 bytes, checksum: b29c60407d282d9848bdfc887c1a97c8 (MD5) / Made available in DSpace on 2018-04-04T19:31:40Z (GMT). No. of bitstreams: 1 ramosjunior_ra_me_bauru.pdf: 2202514 bytes, checksum: b29c60407d282d9848bdfc887c1a97c8 (MD5) Previous issue date: 2018-02-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho traz o estudo das propriedades óticas, elétricas e morfológicas do material TiO2 de forma individual e acoplado com SnO2 dopado com 4at%Sb, formando uma heteroestrutura. Tanto TiO2 quanto a heteroestrutura foram trabalhados na forma de filmes finos depositados pelo método sol-gel-dip-coating, e, no caso do TiO2 também foi relevante sua análise em forma de pós prensados (pastilhas). No que diz respeito ao SnO2:4%Sb, este trabalho traz uma revisão literária de suas principais propriedades, buscando apresentar um panorama geral, pois com isto pode-se entender melhor os fenômenos que ocorrem na heteroestrutura. Os resultados das pastilhas de TiO2 indicam uma transição parcial de fase anatase/rutilo para tratamentos térmicos entre 500ºC e 1000ºC, confirmadas pela fotoluminescência, que apresentou bandas relacionadas a fase anatase ou rutilo, dependendo do processamento utilizado. Filmes de TiO2 mostraram boa foto sensibilidade, com a corrente elétrica respondendo imediatamente à excitação independente da energia, além de um rápido decaimento com relação ao valor excitado. Fora isto, medidas de decaimento da corrente foto induzida, realizadas em atmosfera de O2, indicaram que o decaimento se torna ainda mais rápido na presença do gás, estando associado ao aprisionamento de portadores de carga pelas moléculas adsorvidas na amostra, além da recombinação dos pares elétron-buraco. Com relação à heteroestrutura, quando a condução ocorre preferencialmente no TiO2, a amostra apresenta resultados muito similares às dos filmes de TiO2, tendo uma rápida resposta à excitação com fonte de luz acima do bandgap do TiO2 e um rápido retorno para seu estado de equilíbrio, no escuro. Entretanto, em atmosfera gasosa, o decaimento se torna muito mais rápido, o que também está associado ao aprisionamento de portadores pelas moléculas adsorvidas de gás. Porém, o aumento na taxa com que isto acontece, está relacionado à formação da heteroestrutura e às compensações de carga na interface, que podem ocorrer quando a excitação utiliza comprimento de onda adequado. A configuração lado a lado da heteroestrutura mostrou emissão Poole – Frenkel para tensões maiores que 40V, e quando irradiada com luz que simula o espectro solar apresentou uma região de resistência negativa para algumas potências de excitação que pode estar ligada ao aprisionamento de elétrons na interface. Desta forma, este trabalho visa trazer uma contribuição importante à compreensão do mecanismo de transporte elétrico dos materiais estudados. Por fim, pode-se dizer que os materiais aqui estudados podem ser aplicados como sensores de gás ou dispositivos retificadores/amplificadores desde que seja escolhida a melhor configuração para a aplicação desejada. / This work presents a study of the optical, electrical and morphological characterization of TiO2 thin films, deposited individually or coupled with SnO2 doped with 4at%Sb, forming a heterostructure. Both sort of samples, TiO2 and the heterostructure were studied in thin film form, deposited by sol-gel-dip-coating, and, in the case of TiO2, it was relevant the analysis of samples also in the form of pellets form (pressed powders). With regards to SnO2:4%Sb, this work brings a literary revision of its principal properties, trying to present a general overview, for the better understanding of the phenomena that occur in the heterostructure. The results of TiO2 pellets indicates a partial anatase/rutile phase transition to thermal annealing between 500 and 1000ºC, confirmed by the photoluminescence that presented bands related to anatase or rutile, depending the utilized processing. TiO2 films showed fair photo-sensibility, with immediate response on the electric current to light excitation, independent on the utilized energy, along with fast decay in relation to the excited value. Moreover, photo-induced current decay measurements, performed in O2 atmosphere, indicated that the decay becomes faster in gas presence, being associated to charge carriers trapping by the adsorbed molecules on sample, besides the electron-hole recombination. Concerning the heterostructure, when the conduction occurs preferentially in TiO2 layer, the sample shows very similar results to the TiO2 films, with a fast response to light excitation above the TiO2 bandgap and fast return to the equilibrium state, in dark. However, in gas atmosphere, the decay becomes much faster, which is also associated to the carriers trapping by the gas adsorbed molecules. Nevertheless, the rate increase in this phenomenon is related to the heterostructure formation and the charge compensations at the interface, which may occur when appropriate wavelength is used for excitation. The side by side heterostructure sample showed a Poole – Frenkel emission to bias higher than 40V, and presented a negative resistance region to some irradiation power when illuminated with solar light that can be associated to electrons trapping at the interface. In summary, this work aims to bring a contribution related to the electric transport mechanism of the studied materials. The materials investigated here may be applied in gas sensors or rectifiers/amplifiers devices, according the sample configuration. / CAPES: 1578735

The chemical industry is an essential part of modern society and therefore has a responsibility to develop solutions for the problems facing it. A major problem is continuing to match the material demands of a growing global population whilst simultaneously decreasing the consumption of finite natural resources and limiting the emissions of greenhouse gasses. An optimised catalytic system that shortens, or intensifies, the process chain for the production of chemicals can be an effective solution to this challenge. Auto-tandem catalysis is where a single metal-ligand complex facilitates two or more sequential transformations. For example: alkenes are hydroformylated into aldehydes which are then hydrogenated into alcohols. The alcohols have use as plasticisers or surfactants for metal extraction. A previously reported auto-tandem catalysis system was shown to be capable of sequential hydroformylation-hydrogenation of 1-octene to nonanol. It consisted of the neutral rhodium precursor [Rh(acac)(CO)2] and the bidentate ligand xantphos in 10% iPrOH/H2O co-solvent at temperatures of 160°C. Investigations, reported in this thesis, revealed that xantphos type ligands, with their large bite-angle, and high temperatures are required to generate the hydrogenation activity. However, in contrast to the previous system, water is not necessary; with the same results produced in toluene:iPrOH solutions and water:iPrOH solutions. It is proposed that the iPrOH or H2O has a direct influence in the catalytic cycle, either as a hydrogen-shuttle or generates a cationic rhodium species, known to be active in hydrogenation. High temperature NMR studies show the standard resting state of the hydroformylation catalyst is still predominant at high temperatures therefore the proposed catalytic cycle starts from this step. A recurring problem in the industrial process chain is the separation of the catalyst from the final products. Combing a TiO2 ceramic membrane with a POSS (polyhedral oligomeric silsesquioxane) modified tin catalyst and phosphonium iodide co-catalyst, for the coupling of epoxides and CO2 to make cyclic carbonates, was investigated. The catalyst system showed good substrate compatibility for a range of epoxides. In a prototype membrane set-up the system demonstrated a long catalyst life time, however significant leaching was also observed.

O presente trabalho tem o objetivo de investigar a obtenção de hidrogênio a partir de soluções de etanol em água, por fotocatálise, usando-se catalisadores a base de óxido de zinco (ZnO). Nestes estudos foram empregados cinco catalisadores ZnO, sendo um comercial e os demais preparados através de diferentes metodologias encontradas na literatura. Os catalisadores foram caracterizados por área BET, DRX e FRX, e a investigação preliminar da atividade destes catalisadores foi feita através de ensaios de degradação fotocatalítica de rodamina B em reator slurry em batelada, onde foram avaliadas a taxa de reação e a remoção de corante. Os ensaios para a produção fotocatalítica de hidrogênio foram realizados em um reator de quartzo, operado em batelada com catalisador em suspensão e atmosfera inerte de nitrogênio. A solução foi irradiada por uma série de seis lâmpadas compactas de luz negra. Ao longo dos testes, amostras das fases líquida e gasosa foram coletadas e analisadas para identificação do consumo de etanol e produção de hidrogênio usando-se, respectivamente, Carbono Orgânico Total (TOC) e Cromatografia Gasosa (GC). Resultados preliminares mostraram que os catalisadores ZnO comercial e sintetizado (ZnO Merck e ZnO-B) apresentam atividade fotocatalítica e desempenho similares aos do TiO2 para a degradação da rodamina B. Contudo, estes mesmos catalisadores mostraram-se pouco ativos para a produção fotocatalítica de hidrogênio, com desempenho bastante inferior ao do TiO2 nas mesmas condições. Foi possível observar que o maior rendimento em hidrogênio ocorre para baixas concentrações de catalisador (0,05 gL[elevado a potência menos]1) e elevadas concentrações de etanol, sendo pouco dependente do pH. / This work aims to investigate the hydrogen production from ethanol-water solutions through photocatalysis, using zinc oxide catalysts (ZnO). Five ZnO catalysts were employed in this work; one was a commercial catalyst, while the others were prepared according to different methodologies reported in the literature. The catalysts were characterized by BET, XRD and XRF, and the preliminary investigation of their activity was done by photocatalytic degradation of rhodamine B, through the evaluation of the reaction rate and dye removal. Tests for photocatalytic hydrogen production were carried out in a quartz slurry batch reactor under nitrogen, irradiated by a set of six compact UV light bulbs. During the tests, gas and liquid samples were collected and analyzed in order to identify the consumption of ethanol and hydrogen production using, respectively, Total Organic Carbon (TOC) and Gas Chromatograph (GC). Preliminary results showed that the synthesized and commercial ZnO catalysts (ZnO-B and ZnO Merck) present photocatalytic activity and performance similar to TiO2 for the rhodamine B degradation. However, the ZnO catalysts presented lower performance when compared with TiO2 for hydrogen production, under the same conditions. It was observed that the highest hydrogen yield occurs for low concentrations of catalyst (0.05 gL1) and high concentrations of ethanol, being less dependent on pH.

Nos últimos anos, a utilização de nanotubos (Nts) de dióxido de titânio (TiO2) têm atraído interesse tecnológico e científico de forma significativa devido às suas propriedades únicas, tais como grande área de superfície específica, alta capacidade de absorção e apresentam excelentes atividades fotoeletroquímicas e um meio para melhorar essas propriedades está relacionada ao controle da morfologia dos Nts durante a sua sintetização no processo de anodização. O objetivo desse estudo é avaliar a influência do potencial aplicado durante o processo de anodização para obtenção de Nts de TiO2, tendo em vista a utilização desses nanotubos como catalisador fotoeletroquímico. Para que houvesse a cristalização do óxido, realizou-se tratamento térmico a 400 °C ao ar, durante 3 h com taxa de aquecimento de 10 °C / min. Analisou-se a relação do potencial aplicado durante o processo de anodização com a morfologia dos nanotubos e a sua resposta fotoeletroquímica. As caracterizações foram realizadas através das técnicas de microscopia eletrônica de varredura com emissão de campo (MEV-FEG), difração de raios X (DRX), espectrofotometria no ultravioleta visível (UV-VÍS), voltametria linear e espectroscopia de impedância eletroquímica (EIE).Observou-se que o potencial de anodização exerce influência na geometria do nanotubo, isto é, no comprimento, na espessura da parede e no diâmetro, alterando a absorção de luz e, consequentemente, o desempenho fotoeletroquímico das amostras. Os resultados obtidos por espectroscopia de impedância eletroquímica mostraram pouca diferença na resistividade das amostras estudas. Contudo, as correntes desenvolvidas no ensaio de voltametria linear, indicaram que a amostra Nt30 é um fotoeletrodo promissor para formar heteroestruturas baseado em nanotubos de dióxido de titânio. / In recent years, the use of TiO2 nanotubes (Nts) has attracted technological and scientific interests in a significant way due to its unique properties, such as large specific surface area, high absorption capacity and excellent photoelectrochemical activities. One way to improve these properties is to control the nanotubular morphology during its synthesis through the anodizing process. The objective of this study is to evaluate the influence of the applied potential during the anodization process to obtain titanium dioxide (TiO2) nanotubes and applying these nanotubes as a photoelectrochemical catalyst. In order to crystallize the Nts, heat treatment was carried out at 400 ° C in air for 3 h at a heating rate of 10 ° C / min. The effect of the applied potential during the anodizing process on the morphology of the nanotubes and their photoelectrochemical response were analyzed. The characterization was carried out using scanning electron microscopy (SEM), X-ray diffraction (XRD), visible ultraviolet spectrophotometry (UV-VIS) and electrochemical impedance spectroscopy (EIS). It was observed that the anodization potential influences the geometry of the nanotubes, that is, their length, wall thickness and diameter, altering their light absorption properties; consequently, influencing the photoelectrochemical performance of the samples. The results obtained from the electrochemical impedance spectroscopy showed a slightly small difference in the charge transportation resistance of the studied samples. However, the currents developed in the linear voltammetry tests indicated that the Nt30 sample is a promising photoelectrode to apply for other applications such as heterostructures and cationic/anionic doped structures based on titanium dioxide nanotubes.