Recentemente tem sido observado grande avanço na área de fotovoltaicos orgânicos e híbridos. Esses dispositivos baseiam-se em diferenças de energia eletrônica nas interfaces dos componentes de uma heterojunção, onde as heterojunções dispersas obtidas via arranjos interpenetrantes com estes dois compostos, em dimensões sub-20-nm, permite coleção efetiva dos portadores de carga fotogerados, mesmo com pequeno comprimento de difusão do éxciton e baixa mobilidade dos portadores de carga. Desta maneira, o estudo e a modificação da interface entre as duas fases é essencial para melhorar a eficiência de conversão desses dispositivos. Este trabalho tem como objetivo investigar heterojunções de dióxido de titânio (TiO2)/poli(3-hexil tiofeno) (P3HT) como camadas ativas em dispositivos fotovoltaicos híbridos. Essas heterojunções são atraentes para fotovoltaicos híbridos por permitir a nanoestruturação do metalóxido antes da incorporação do polímero, levando à obtenção de elevada área interfacial e com a possibilidade de ajustar as propriedades interfaciais mantendo o caráter aceitador/doador desta heterojunção. Os filmes de TiO2 foram obtidos a partir de dispersões coloidais de nanopartículas de anatase, enquanto aqueles de P3HT foram obtidos a partir de sua solução de 1,2-diclorobenzeno. Como eletrodos foram utilizados o óxido de índio dopado com óxido de estanho (ITO) e ouro (Au). A caracterização elétrica e espectroscópica indicou que os parâmetros fotovoltaicos, bem como absorção e fotoluminescência, dependem da submissão dos dispositivos a tratamentos térmicos post-production, evidenciando que o aquecimento induz a mudanças conformacionais no polímero, alterando a interface óxido/polímero. A introdução de grupos carboxilato nas ramificações 3-hexil do P3HT permite melhor contato entre óxido/polímero, sendo favorecido por tratamento térmico. Mais ainda, a infiltração do polímero em filmes de TiO2 nanocristalino levou à obtenção de dispositivos fotovoltaicos de considerável estabilidade, apresentando atividade mesmo após 6 meses após a elaboração destes. Finalmente, neste trabalho também é proposta a utilização de um complexo a base de ftalocianina de zinco como modificador de interface do TiO2, cuja absorção estende a janela espectral do dispositivo até o vermelho e infravermelho próximo. Estudos de fenômenos de transporte, levando-se em conta a fotogeração de portadores e sua recombinação, foram realizados por medidas do espectro de fotocondução no dispositivo / Recently a fast development in organic and hybrid photovoltaic field has been observed. Such devices are fabricated by organic semiconductors within components of a heterojunction, in which bulk heterojunctions obtained via interpenetrating networks at the sub-20-nm length scale. It permits the effective collection of photogenerated charge carriers even with low exciton diffusion length and low charge carrier mobilities. Therefore, the study of material properties and the interface modification are essential to improve the power efficiency of such devices. The goal of this work is to investigate heterojunctions of titanium dioxide (TiO2) and poly(3-hexyl thiophene) (P3HT) as active layers in hybrid photovoltaic devices. Such heterojunctions are attractive since the metaloxide can be nanostructured previous the infiltration of the polymer within the nanocrystalline phase, leading on large interfacial area with the possibility to tune the interfacial properties keeping the acceptor/donor character of the two components. Titania films were obtained from colloidal dispersions of anatase nanoparticles, while P3HT from its solution in 1,2-dichlorobenzene. The electrodes were indium-tin oxide (ITO) and gold (Au). Electrical and spectroscopic characterization shows the photovoltaic parameters, as well as absorption and photoluminescence, depends on post-production treatments, evidencing that heating induces conformational changes in the polymeric phase, changing the oxide/polymer interface. The introduction of carboxyl groups at 3-hexyl ramifications in P3HT permits better contacts between oxide and polymer by chemisorption, being favored by thermal treatment. Furthermore, the infiltration of the polymer within the nanocrystalline TiO2 leads on enhanced stability of the devices, working even six months after their preparation. Finally, in this work is also proposed the utilization of a interface modifier based on zinc phtalocyanine complex, which has extended the device absorption window up to the red/ near infrared, increasing light harvesting, and a transport study related to photocarriers generation and recombination process was carried out by photoconductivity action spectra

Grâce à ses propriétés optiques originales, une NanoParticule d’Or (NPO) excitée peut se comporter comme une nano-source de lumière, de chaleur et d’électrons chauds. Ces propriétés plasmoniques remarquables sont exploitées dans de nombreuses transformations chimiques. Dans ce contexte, la photocatalyse plasmonique basée sur le transfert d’électrons entre une NPO et un semi-conducteur a été proposée. Cependant, peu d’études sont centrées sur l’influence du plasmon et la contribution respective de ses effets locaux (thermiques et électroniques) sur ce transfert utilisé en photocatalyse. Ici, nous abordons ces problématiques à travers 3 réactions catalytiques. Premièrement, nous montrons la faisabilité de l'oxydation efficace et sélective de glycérol sans aucune source externe de chaleur grâce à l’effet thermoplasmonique local de la NPO. Nous étudions ensuite la dégradation de bisphénol-A sur différents supports catalytiques. Nos résultats montrent que la NPO joue un rôle primordial à travers le transfert d’électrons mais aussi en tant que nano-source de chaleur permettant d’accélérer la cinétique et d’éliminer ainsi totalement et rapidement ce perturbateur endocrinien. Enfin, nous avons développé un montage optique pour étudier la dégradation de polluants à l'échelle nanométrique. Pour cela, nous avons réalisé un système hybride à base de NPOs couplées à un nanofilm de TiO2 par structuration laser. Nos travaux montrent que l’activité catalytique est corrélée aux dimensions structurales des NPOs. Ces résultats ouvrent la voie vers l'exploitation de nombreux processus industriels sous lumière solaire / The excitation of Localized Surface Plasmon Resonance (LSPR) of Gold NanoParticles (GNPs) can give many physical effects such as near-field enhancement, heat generation and hot electron injection, which have been investigated in many chemical transformations. In that context, the plasmonic photocatalysis based on electron transfer from GNP to a semi-conductor has been proposed. However, few studies are focused on the influence of LSPR features and the respective contribution of its local effects (thermal and electronic) on the photocatalytic activity. These issues are addressed herein through 3 catalytic reactions. First, the efficient and selective oxidation of glycerol in the presence of supported GNPs is demonstrated under laser irradiation and without any external source of heat, thanks to the local heat generation and hot electron transfer. The respective contributions of these effects is further investigated in plasmonic photocatalysis by following the degradation of Bisphenol-A. Our results show that GNP plays a major role through hot electron transfer but also as a nano-source of heat that accelerates the reaction and leads to a fast and total elimination of this endocrine disruptor. Finally, an optical set-up is developed for studying the plasmonic photocatalysis at the nanoscale. For this, a hybrid system of GNPs coupled to a TiO2 nanofilm is realized by laser nanostructuring. Our investigations show that photocatalytic activity is correlated to the LSPR (size and shape of GNPs, hot spots). These results open the way for exploiting valuable and industrial reactions under solar light

Orientador: Luís Augusto Sousa Marques da Rocha / Resumo: O titânio (Ti) é um material que apresenta boa resistência à fadiga e à corrosão. Ainda que seja utilizado na fabricação de próteses ortopédicas e implantes dentários, o titânio metálico não é bioativo, ou seja, não é capaz de provocar reações que favoreçam a fixação de implantes, biocolonização ou a regeneração de tecidos, além de apresentar alguns inconvenientes relacionados a propriedades de superfície, que podem levar à sua degradação. Para fins biomédicos, essa degradação se dá principalmente por processos de tribocorrosão, que ocorre quando ações mecânicas e químicas acontecem de formas concomitantes. Diante deste cenário, superfícies de titânio (Ti) foram recobertas com filmes finos de óxido de titânio (TiO2) por meio da técnica de Sputtering reativo. O principal objetivo do trabalho foi entender como as fases anatase e rutilo dos filmes de TiO2, produzidos por sputtering reativo, podem influenciar na resistência dessas superfícies de titânio, recobertas, à tribocorrosão. São apresentadas análises estruturais e de composição desses filmes, a partir de difração de raios-X e espectroscopia Raman, que confirmam a obtenção de filmes finos compostos de diferentes proporções entre as fases anatase e rutilo, além de uma análise detalhada da forma de crescimento, a partir de microscopia eletrônica de transmissão (MET). O trabalho apresenta uma análise da resistência dos filmes finos de TiO2 no que diz respeito aos mecanismos de tribocorrosão, em meios fisiológicos. Nesse senti... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Titanium (Ti) is a material that has good resistance to fatigue and corrosion. Although it is used in the manufacture of orthopedic prostheses and dental implants, metallic titanium is not bioactive, that is, it is not capable of causing reactions that favor the fixation of implants, biocolonization or tissue regeneration, in addition to presenting some inconveniences related to surface properties, which can lead to its degradation. For biomedical purposes, this degradation occurs mainly through tribocorrosion processes, which occur when mechanical and chemical actions occur in concomitant ways. In view of this scenario, titanium (Ti) surfaces were covered with thin films of titanium oxide (TiO2) using the reactive Sputtering technique. The main objective ofthe work was to understand how the different phases present in TiO2films, anatase and rutile, can influence the resistance of these surfaces relatedto tribocorrosion.Structural and composition analyzes of these films are presented, using X-ray diffraction and Raman spectroscopy, which confirm the achievement of thin films composed of different proportions between the anatase and rutile phases. Inaddition, a detailed analysis of the growth morphology was performed using transmission electron microscopy (TEM). The work presents an analysis of the resistance of TiO2thin films with respect to tribocorrosion mechanisms, in physiological media. In this sense, the tribocorrosion tests were carried out, the electrochemical data ar... (Complete abstract click electronic access below) / Doutor

Titanium dioxide (TiO2) is an important semiconducting metal oxide and is expected to play an important role in future applications related to photonic crystals, energy storage, and photocatalysis. Two aspects regarding the combustion synthesis have been investigated; scale-up in laboratory synthesis and advanced nanoparticle synthesis. Concerning the scale-up issue, a novel curved wall-jet (CWJ) burner was designed for flame synthesis. This was achieved by injecting precursors of TiO2 through a central port into different flames zones that were stabilized by supplying fuel/air mixtures as an annular-inward jet over the curved wall. This provides a rapid mixing of precursors in the reaction zone with hot products. In order to increase the contact surface between the precursor and reactants as well as its residence time within the hot products, we proposed two different modifications. The CWJ burner was modified by adding a poppet valve on top of the central port to deliver the precursor tangentially into the recirculating flow upstream within the recirculation zone. Another modification was made by adopting double-slit curved wall-jet (DS-CWJ) configuration, one for the reacting mixture and the other for the precursor instead of the central port. Particle growth of titanium dioxide (TiO2) nanoparticles and their phases were investigated. Ethylene (C2H4), propane (C3H8), and methane (CH4) were used with varying equivalence ratio and Reynolds number and titanium tetraisopropoxide (TTIP) was the precursor. Flow field and flame structure were quantified using particle image velocimetry (PIV) and OH planar laser-induced fluorescence (PLIF) techniques, respectively. TiO2 nanoparticles were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman Spectroscopy, and BET nitrogen adsorption for surface area analysis. The flow field quantified by PIV consisted of a wall-jet region leading to a recirculation zone, an interaction jet region, followed by a merged-jet region. The modified CWJ burner revealed appreciable mixing characteristics between the precursor and combustion gases within these regions, with a slight increase in the axial velocity due to the precursor injection. This led to more uniformity in particle size distribution of the synthesized nanoparticles with the poppet valve (first modification). The double-slit modification improved the uniformity of generated nanoparticles at a very wide range of stable experimental conditions. Images of OH fluorescence showed that flames are tightly attached to the burner tip and TTIP has no influence on these flames structures. The particle size was slightly affected by the operating conditions. The phase of TiO2 nanoparticles was mainly dependent on the equivalence ratio and fuel type, which impact flame height, heat release rate and high temperature residence time of the precursor vapor. For ethylene and methane flames, the anatase content is proportional to the equivalence ratio, whereas it is inversely proportional in the case of propane flames. The anatase content reduced by 8% as we changed Re between 8,000 and 19,000, implying that the Re has a slight effect on the anatase content. The synthesized TiO2 nanoparticles exhibited high crystallinity and the anatase phase was dominant at high equivalence ratios (φ >1.6) for C2H4, and at low equivalence ratios (φ <1.3) for the C3H8 flame. Concerning advanced nanoparticle synthesis, a multiple diffusion burner and flame spray pyrolysis (FSP) were adopted in this study to investigate the effect of doping/coating on TiO2 nanoparticles. The nanoparticles were characterized by the previously mentioned techniques in addition to thermogravimetric analysis (TGA) for carbon content, X-ray photoelectron spectroscopy (XPS) for surface chemistry, ultraviolet-visible spectroscopy (UV-vis) for light absorbance, inductively coupled plasma (ICP) for metal traces, and superconducting quantum interference device (SQUID) for magnetic properties. Results from multi diffusion burner show that doping TiO2 with vanadium changes the phase from anatase to rutile while doping and coating with carbon or SiO2 does not affect the phase. Doping with iron reduces the band gab of TiO2 particles by reducing the conduction band. FSP results show that iron doping changes the valance band of the nanoparticles and enhances their paramagnetic behavior as well as better light absorption than pure titania, which make these particles good candidates for photocatalytic applications.

The aim of this paper is to summarize and evaluate properties of polymers modified modified mortar, their durability and the possibility of surface treatment. Recently, the requirements for additional surface treatment of architectonal concrete are increased and the application of polymer-modified mortar can accelerate and simplify the realization of visible concrete. Polymer-modified mortar with the addition of powder photocatalysts can significantly reduce and thus increase the availability of photoactive concrete structures. The experimental part deals with the addition of photocatalyst to the polymer-modified mortar and the subsequent assessment of the photocatalytic properties, the possibility of modification cement mortars with anorganic pigments and the application of transparent coatings for the enhancement of color saturation and resistance.

This diploma thesis deals with photoelectrochemical cells containing photoactive titanium dioxide anode and their use for photocatalytic degradation of organic compound from water solutions. The electrical properties of the produced photoelectrochemical cells were determined by the use of voltamperometric characteristics, the oxidation ability of the cells was monitored by measuring the fluorescence of the oxidative intermediates. To study these reactions, benzoic acid was used as the fluorescence probe for OH˙ radicals. The aim of the study was to study the influence of material composition and spatial arrangement of the cathode and the relationship between irradiation, current and rate of electrode processes.

This diploma thesis deals with matte coatings for optical 3D scanning. The aim of this thesis is to find a method of spraying the mixture of TiO2 and ethanol that would provide layer thickness beyond the measurable range of the 3D scanner. A spray gun allowing deposition of atomized mixture was design. The coatings created by this gun and by airbrush gun, which is commonly used for this purpose, were compared. The matting effect, thickness and the influence of used TiO2 particles were investigated in the coatings. The paper shows method of applying coatings that ensure sufficient matting of the surface for scanning purposes, and simultaneously have thicknesses that should not affect scanning results.

The diploma thesis deals with photocatalytic degradation of organic polutants on water- suspended UV activated anatase particles. The measurements are executed on a pilot plant UV photoreactor and the aim the thesis is to figure out the time course of azo dyes degradation under different photoreactor settings and subsequently infer the effectivity of the photoreactor under different settings. The degree of the aze dyes degradation is evaluated via UV-VIS spectrometry.

This thesis deals with the construction of a photoelectrochemical cell, which is used for detection of ultraviolet radiation by means of generated photocurrent in dependence on the intensity of incident radiation. The cell construction is based on a carbon electrode system with a titanium dioxide sensory layer and a UV curable electrolyte. Printing techniques such as screen printing, inkjet printing and pad printing were used to deposit individual layers. Carbon electrodes with sensory layer were studied through profilometric analysis, optical microscopy, and four-point probes. The viscosity of the liquid formulation of uncured electrolyte was characterized by rheometric measurement. Photoelectrochemical properties of the prepared cell for use as a UV sensor were investigated by cyclic voltammetry and chronoamperometry.

This diploma thesis is focused on the study of the effect of ultraviolet radiation and titanium dioxide on the yeast Candida vini. Photocatalytic inactivation of this yeast was performed on various types of titanium dioxide films, which were immobilized on soda lime glasses. Acridine orange was used as a dye to distinguish live and dead yeast cells after certain irradiation time. Live and dead cells emit different light in colour after staining in acridine orange. Candida vini photocatalytic inactivation depends on the amount of titanium dioxide immobilized on glass as well as on the structure of its surface if the lamp intensity remains the same. Kinetics of this photocatalytic process was studied, too.