Wide band gap metal oxides have recently become one of the most investigated materials in surface science. Among these metal oxides especially TiO2 attracts great interest, because of its wide range applications, low cost, biocompatibility and ease of analysis by all experimental techniques. The usage of TiO2 as a component in solar cell technology is one of the most investigated applications of TiO2 . The wide band gap of TiO2 renders it inecient for isolated use in solar cells. TiO2 surface are therefore coated with a dye in order to increase eciency. This type of solar cells are called dye sensitized solar cells . The eciency of dye sensitized solar cells is directly related with the absorbed light portion of the entire solar spectrum by the dye molecule. Inspite of the early dyes, recent dye molcules, which are called wider wavelength response dye molecules, can absorb a larger portion of entire solar spectrum. Thus, the eciency of dye sensitized solar cells is increased by a considerably amount. In this thesis the electronic structure of organic rings, which are the fundamental components of the dye molecules, adsorbed on anatase (001) surface is analyzed using density functionaltheory. The main goal is to obtain a trend in the electronic structure of the system as a function of increasing ring number. Electronic structure analysis is conducted through band structure and density of states calculations. Results are presented and discussed in the framework of dye sensitized solar cells theory.

Titanium dioxide (TiO2), a semiconductor, has been used in many areas like heterogeneous photocatalysis. In the present study, the effect of hydrothermal treatment conditions and the use of carbon nanotubes on the photocatalytic activity of sol-gel synthesized titanium dioxide were examined. The anatase particles were transformed into layered trititanate particles with either nanotube or nanoplate structure by hydrothermal treatment under the alkaline conditions. Post hydrothermal treatment under neutral conditions was also applied and mesoporous particles were transformed into nanostructured, highly crystalline and ordered anatase particles. Photocatalytic activities of hydrothermally treated samples were determined against Escherichia coli under solar irradiation. Results showed that hydrothermal treatment under alkaline conditions improved the photocatalytic activity. However, although being highly crystalline, after post treatment, a limited activity was obtained because of dehydration of active (101) face of anatase. Nevertheless, TiO2&amp / #8217 / s initial inactivation constant rose from 0.6 to 2.9 hr-1 after regeneration of active sites in aqueous medium under solar irradiation. In order to enhance the surface area and improve activity, multi-walled carbon nanotubes were utilized during the synthesis of TiO2. The effect of calcination conditions and presence of sodium, iron and cobalt on the photocatalytic activity were also studied. For these samples, photocatalytic activities were tested with methylene blue solution under UV irradiation. It was observed that the utilization of CNTs enhanced both the surface area and the activity. Compositions with highest CNT content had better activities for their ability to delay charge recombination. While pure TiO2&amp / #8216 / s initial decomposition constant was 0.8 hr-1, with sodium doping the best value of 1.9 hr-1 was achieved.

Energy need in transportation and industry is mainly met by fossil fuels. This causes consumption of resources and some environmental problems. Diesel and gasoline engines are developed to consume fuel efficiently in vehicles. Since these engines work in a low fuel to air ratio, it becomes difficult to reduce nitrogen oxide emission. For this reason NO x storage/reduction (NSR) catalysts have been developed. While engines are operating under lean conditions alkaline or alkaline-earth component of NSR catalysts capture nitrogen oxides and during fuel rich period stored nitrates are reduced to nitrogen and oxygen gases. To develop this technology, different system parameters, for example system components and reaction environments have been widely investigated experimentally. To supplement the experimental findings, binding energies and structural properties of NO x on different catalyst components have been investigated theoretically. It has been experimentally observed that adding TiO2 to other conventional support materials increases resistance against sulfur poisoning, which is one of the main problems concerning NSR catalysts. For this reason, in this thesis (001) and (101) anatase surfaces have been investigated. Moreover, the effects of barium oxide units and layers on the electronic properties of the (001) anatase surface have been studied. To observe the effects of TiO2 as a support component, interactions of NO2 and SO2 on the unsupported and anatase supported (100) BaO surfaces have been compared. A clear increase in sulfur resistance has been observed in the presence of TiO2 in the catalyst under certain conditions.

In this work the electronic and structural properties of anatase TiO2 (100) surface and gold adsorption have been investigated by using the first-principles calculations based on density functional theory (DFT). TiO2 is a wide band-gap material and to this effects it finds numerous applications in technology such as, cleaning of water, self-cleaning, coating, solar cells and so on. Primarily, the relation between the surface energy of the anatase (100)-1x1 phase and the TiO2-layers is examined. After an appropriate atomic layer has been chosen according to the stationary state of the TiO2 slab, the adsorption behavior of the Au atom and in the different combinations are searched for both the surface and the surface which is supported by a single Au atom/atoms. It has been observed that a single Au atom tends to adsorb to the surface which has an impurity of Au atom or atoms. Although, the high metal concentration on the surface have increased the strength of the adsorption, it is indicated that the system gains a metallic property which is believed to cause problems in the applications. In addition, the gold clusters of the dimer (Au2) and the trimer (Au3) have been adsorbed on the surface and their behavior on the surface is investigate. It is observed that the interaction between Au atoms in the atomic cluster each other is stronger than that of gold clusters and the surface.

Afin d'étudier la granulo- et la morpho-dépendance des propriétés d'énergies de surface de solides divisés, plusieurs lots de TiO2 anatase ont été synthétisés. Une série de matériaux parfaitement définis avec des morphologies allant de sphéroïdale à facettée, dans des gammes de tailles allant de 4 à 20 nm a été obtenue grâce aux modifications de conditions de pH et la présence d'acides organiques. La combinaison de différentes molécules sonde a permis de déterminer l'hétérogénéité énergétique superficielle de ces matériaux, aux interfaces solide/gaz et solide/liquide. La volumétrie de quasi-équilibre à basse pression (N2/Ar) couplée à la méthode de modélisation DIS et la microcalorimétrie à écoulement de gaz (NH3) ont mis en évidence les contributions des différentes faces cristallographiques et les effets de la cristallinité. Ces mêmes propriétés ont été analysées grâce à la titration potentiométrique en milieu aqueux (H+/OH-), couplée à la procédure TDIS (détermination du PCN et des distributions d'affinité de protons). Cette stratégie a permis une étude complète des propriétés superficielles énergétiques et géométriques des nanomatériaux. / In order to study the relationships between the particle size, the morphology and the surface energy properties of divided solids, several batches of TiO2 anatase were synthesized. A series of materials with morphologies ranging from spheroidal to well faceted, with particle sizes ranging from 4 to 20 nm were obtained by adjusting the pH conditions and the presence of organic acids. The surface heterogeneity of these materials, at solid/gas and solid/liquid interfaces, was studied by combining various molecular probes. The low pressure quasi-equilibrium adsorption volumetry (N2/Ar) coupled with the DIS modeling approach and the flow adsorption microcalorimetry (NH3) have evidenced the various contributions of crystallographic faces and the effect of the crystallinity. These properties have also been analyzed using potentiometric titration in aqueous medium (H+/OH-), coupled with the TDIS procedure, to determine PZC and proton affinity distributions. Such a strategy has led to a complete study of the energetic and geometric surface properties of these nanomaterials.

Master’s thesis deals with synthesis of anatase and its anion doping by carbo-nitridation. Prepared samples were used for testing of the photocatalytic activity. Low-temperature anatase was synthesized at 80 °C for 6 hours and carbo-nitridatation was carried out in ammonia/tetrachloromethane atmosphere at 500 °C for 3 hours. The influence of silver content on low-temperature crystallization of anatase was studied by reaction of titanium tetraisopropoxide with water. Silver nanoparticles were prepared by reduction of silver nitrate by D-glukose and sodium citrate. One of the results is the draft for one-pot synthesis of anatase by titanium tetraisopropoxide with complexing agent (sodium citrate, ammonium citrate, citric acid). The study of photocatalysis water splitting was carried out in the presence of 20 % vol. of methanol. Anatase prepared with citric acid has the highest photocatalytic activity (Pt 0,5 %) in UV/VIS spectral region. The activity achieved 38,6 % effectiveness of TiO2 standard (Degussa P25). Doping by nitrogen didn’t lead to increase of photocatalytic activity.