This diploma thesis focuses on the photocatalytic effect of titanium dioxide and ultraviolet light. Theoretical part shows the effect of titanium dioxide and aplication in various branches. Antibacterial effect of titanium dioxide iluminated by ultraviolet light was observed in the flow tube reactor on the yeast Hansenula anomala. After adjusting the optimal flow rate experimented with different inicial concentration of yeast cells. To increase desired effect also silver was used in the photocatalytic system. As observed in many previous studies, silver decreases the time needed for killing the microorganisms. The optained date were analysed.

In this diploma thesis, photocatalytic effect of titanium dioxide with addition of silver was described and demonstrated on inactivation of the yeast Candida vini. Titanium dioxide was prepared by sol-gel process and deposited by printing metod on soda-lime glasses. On the deposit of titanium dioxide was added silver in various concentrations which increased effect of TiO2. Inactivation of yeasts was examined by effectiveness of UV light with intensity 170 and 100 W/m2.

Heterogenous photocatalysis using titanium dioxide seems to be a promising method for disposal xenobiotics from the environment. The aim of this diploma thesis is the study of degradation of selected xenobiotics and biologically active substrances applying this method. Theoretical part of diploma thesis deals with the principals of heterogenous photocatalysis by means of a semiconductor TiO2 and the examples of its possible application are mentioned too. The compounds which could be appropriate for a study of degradation were selected from the group of pharmaceuticals and pesticides. The properties of target substances and their environmental impact were described. Furthermore, a bibliographic search focused on the possibilities of their analytical determination was conducted. The experimental part of the thesis describes the experiments with photocatalyst in a form of powder as well as with immobilized photocatalyst in thin layer on a carrier. Identification and quantification of analytes was realized by high performance liquid chromatography with mass spectrometic detection.

The diploma thesis describes monitoring of photocatalytic activity of titanium dioxide thin films and photocatalytic degradation of azo dyes, the degradation was also experimentally researched in thin film with polymer matrix. Suitable dye for construction of optical sensor for UV light was chosen from the rate of the azo dyes fading by UV and VIS light. The bleaching rate of the sensors was influenced by addition of another dye into the composition and also by concentration of photocatalyst, polymer and calibration agents. At the end of this thesis, the reciprocity test of prepared compositions was made.

Tato diplomová práce se zabývá testováním vhodných indikátorových inkoustů k ohodnocení fotokatalytické aktivity. V teoretické části jsem studovala literaturu související s možnostmi stanovování fotokatalytické aktivity a zaměřila se také na kinetiku, kterou je zmíněnou fotokatalýzu možné ohodnotit. V experimentální části jsem mnou vybraná barviva natiskla na skleněný substrát obsahující vrstvu oxidu titaničitého a následně je otestovala. Došlo také k úpravě aparatury, aby bylo možné měřit větší škálu barev. Po otestování a vybrání vhodných barviv jsem se pokusila o optimalizaci podmínek tisku. Nakonec jsem optimalizovala i samotnou aparaturu.

The subject of this theses is a preparation of chemical UV dosimeters working on diverse principles and their printing. Three UV dosimeters were prepared. The first one is based on a photocalalytic reaction of titanium dioxide with redox dyes. Two other dosimeters are based on a reaction of a photolabile substance able to produce an intermediate reacting with a dye. Prepared dosimeter compositions were coated using a material roll-to-roll printing machine on a corona-treated PET foil. Prepared dosimeter compositions were calibrated for desired exposition to UV radiation doses. Validity of a reciprocity law was verified.

This diploma thesis deals with changing properties of the thin layered titanium dioxide dispersion depending on the time of ball-milling. Titanium dioxide is immobilized on glass or conductive glass using the spin-coating method and the prepared thin layers are then characterized by various analytical methods. All of used analytical methods are described in theoretical and experimental sections, these methods include scanning electron microscopy, profilometry, dynamic light scattering, integrating sphere, ellipsometry, BET isotherm, voltammetry and chronoamperometry. At the summary of this diploma thesis is described how the properties of titanium dioxide thin layers change during ball-milling process.

Le dioxyde de titane suscite un grand intérêt dans le domaine de la photocatalyse. Cependant, il n'utilise que la composante UV du flux solaire soit 4-5 % de l'énergie disponible. Un objectif de cette thèse est d'élaborer un matériau capable d'absorber dans le visible tout en restant actif sous lumière UV. Des nanoparticules de dioxyde de titane modifiées avec de l'or et/ou de l'azote ont été synthétisées par pyrolyse laser. Les poudres obtenues ont été caractérisées systématiquement par différentes techniques physico-chimiques (analyse ICP-AES), structurales (DRX), morphologiques et texturales (MET, MEB, BET), optiques (Spectroscopie UV-Visible) et électroniques (XPS, RPE et TRMC). Les particules présentent une structure cristalline majoritairement anatase, avec une taille moyenne de l'ordre de 7-10 nm. Leur efficacité photocatalytique a été évaluée par HPLC vis-à-vis de la dégradation d'acides carboxyliques (C1-C4) sous lumière UV et Visible. Les résultats photocatalytiques obtenus sur un polluant modèle (l'acide formique) ont révélé que sous UV le TiO2 préparé par pyrolyse laser est nettement plus actif que la référence commerciale. La modification à l'or améliore encore l'efficacité en facilitant le transfert de charge, alors que le dopage à l'azote introduit des sites de recombinaison provoquant donc un effet négatif. Ces résultats ont été corrélés à la dynamique des porteurs de charge étudiée par TRMC (Time Resolved Microwave Conductivity). La combinaison des deux élèments Au et N montre une efficacité proche de la référence commerciale, tout en introduisant une activité dans le visible. Dans le cas des acides à plus longue chaîne, la photoactivité des différents photocatalyseurs est proche de la référence commerciale sous lumière UV, mais reste très limitée dans le visible. La compréhension des mécanismes de dégradation a été abordée par la Résonance Paramagnétique Electronique (RPE). / Titanium dioxide is the most widely used photocatalyst due to its amazing properties. However, TiO2 is activated by UV radiation which represent about 4-5 % of solar light. One aim of this work is to shift the adsorption of TiO2 to the visible range while maintaining photoactivity under UV. Therefore N-doped and gold modified TiO2 nanoparticles have been synthesized in one step by laser pyrolysis. The materials have been characterized; their photocatalytic activity was evaluated by the degradation of carboxylic acids (C1-C4) under both UV and Visible irradiation. When dealing with the decomposition of formic acid under UV light, all samples exhibit a higher activity compared to commercial P25. Modification with Au increases the reaction rate by enhancing charge separation, while N-doped sample are less efficient due to recombination centers induced by Nitrogen. These results were correlated to the dynamic of electron/hole pairs studied by TRMC (Time Resolved Microwave Conductivity). Moreover, the combination of Au and N showed an efficiency similar to commercial P25 under UV irradiation associated to photoactivity in the visible range. In the case of C2-C4 acids, photocatalytic performances of all photocatalysts are similar to commercial P25 under UV, but very weak under visible light. Degradation mechanisms were investigated by ESR (Electron Spin Resonance).

abstract: Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties, defects, and how these are controlled via synthesis is essential. Both bulk and nanoscale materials characterization, in addition to various performance metrics, can be combined to elucidate functionality at multiple length scales. In this work, two promising visible light harvesting systems are studied in detail: Pt-functionalized graphitic carbon nitrides (g-CNxHys) and TiO2-supported CeO2-x composites. Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given. In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk/nanoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2019

MSc (Physics) / Department of Physics / Since the discovery of water photolysis on a TiO2 electrode by Fujishima and Honda in 1972, TiO2 has attracted extensive attention as an ideal photocatalytic material because of its excellent properties such as high activity, good stability, nontoxicity and low cost. Hence, it has been widely used in the fields of renewable energy and ecological environmental protection. However, as a wide band gap oxide semiconductor (Eg = 3.14 eV), brookite TiO2 can only show photocatalytic activity under UV light irradiation (λ < 387.5 nm) that accounts for only a small portion of solar energy (approximately 5 %), in contrast to visible light for a major part of solar energy (approximately 45 %). Therefore, effectively utilizing sunlight is the most challenging subject for the extensive application of TiO2 as a photocatalyst. Due to the unique d electronic configuration and spectral characteristics of transition metals, transition metal doping is one of the most effective approaches to extend the absorption edge of TiO2 to the visible light region. This method of doping either inserts a new band into the original band gap or modifies either the conduction band or valence band, improving the photocatalytic activity of TiO2 to some degree. In this work, the structural, electronic and optical properties of doped and undoped TiO2 (100), (110) and (210) surfaces were performed using first principle calculations based on DFT using a plane-wave pseudopotential method. The generalized gradient approximation was used in the scheme of Perdew-Burke-Ernzerhof to describe the exchangecorrelation functional as implemented in the Cambridge Sequential Total Energy Package code in the Materials Studio of BIOVIA. The metal dopants shift the absorption to longer wavelengths and improves optical absorbance in visible and near- IR region. The un-doped (210) surface showed some activity in the visible and near IR region. / NRF