This work investigates the correlation of structural and photovoltaic properties of dyes used in dye-sensitized solar cells. Experimental methods, including ultraviolet-visible spectroscopy, fluorescence spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy are employed to study optical and electrochemical properties of dye molecules. Computational methods, including density functional theory and time-dependent density functional theory, are used to validate and predict the optical and electronic properties of dye molecules, in their isolated state and once embedded into a working electrode device environment that comprises a dye...TiO2 interface. The results chapters begin with the presentation of a series of quinodimethene dyes that are experimentally validated for their photovoltaic application, and associated computational studies reveal that an inner structural factor - a phenyl ring rotation occurring during the optical excitation process - leads to the competitive photovoltaic device performance of these dyes. Carbazole-based dyes are then systematically studied by computation, especially considering charge transfer paths and binding modes of these dyes on a titania surface. The theoretical models for the basic building block of this chemical family of dyes, known as MK-44, successfully support and explain structural discoveries from X-ray diffraction and reflectometry that impact of their function. A benzothiadiazole-based dye, RK-1, is then systematically studied by both experimental and computational methods, and the results show that the π-bridge composed of thiophene, benzothiadiazole and benzene rings leads to excellent charge separation; and the rotation of these rings during the optical excitation process may well be consistent with the fluorescence spectrum. Finally, the well-known ruthenium-based dyes are theoretically studied to determine the properties of different ligands connected to the metal core of the complex. Conformations with different NCS ligands are calculated in terms of energy and explain well the corresponding results from X-ray diffraction. Acid-base properties of carboxyl groups connected to pyridine ligands in N3 and N749 are theoretically calculated based on thermodynamics and density functional theory. Implicit and explicit models are both adopted to predict these acid dissociative constant values, which are generally in a good agreement with the reported experimental data. The thesis concludes with conclusions and a future outlook.

This diploma thesis is focused on the study of the influence of advanced oxidation processes on degradation of organic dyes. The field of AOP – very effective physically-chemical methods of wastewater treatment – includes application of strong oxidation agents, UV and ionizing radiation and electrical discharges. For this thesis, two of these methods were chosen – the application of oxidation agent (ozone) and UV radiation. Along with electrolysis, which is mentioned rather marginally in this thesis (it is the subject of the previous thesis), these phenomena are products of electrical discharge in water, where they participate in the processes of degradation in a different way. For all measurement series, two direct azo dyes were chosen as model substances – C.I. Direct Blue 106 and C.I. Direct Red 79. The ozonizer, in which either oxygen or synthetic or technical air were loaded as carrier gases, was used for degradation of dyes by ozone. The generated ozone was loaded into the bubbling vessel with dye solution of different initial concentration (10–130 mg.dm-3), which was followed by other bubbling vessel with KI solution for the next analytical determination of the amount of generated ozone. The other parameters changed were the gas flow (1–2 dm3.min-1), ozonizer output (minimal and maximal), type of dye, pH value of the solution (neutral or acid) and additional electrolyte (NaCl, Na2SO4 or any). The reactor for the study of the influence of UV radiation on degradation of dyes was an UV sterilizer into which the equivalent volume of dye solution was added. The possibilities of experimental settings were limited and only the type of dye, an additional electrolyte and pH value of the dye solution were adjusted (as in the case of ozone). Several series of samples were measured with various input conditions which more or less influenced the degradation of investigated dyes in this experiment. It was found that for both used methods the Direct Blue 106 dye was more degradable (with significantly better results for ozone than for UV radiation). The degradation of Direct Red 79 dye proceeded only by ozone treatment, in the case of the application of UV radiation no degradation occurred. By investigation of the influence of initial concentration of dye on its degradation, it was confirmed that with the initial concentration enhancement the final concentration rises as well, whereas in low concentrations (10–50 mg.dm-3) the initial concentration has no effect. The addition of an electrolyte had an accelerating effect on dye degradation in both methods (NaCl and also Na2SO4 showed similar results though the degradation proceeded in different ways). The addition of HCl accelerated the degradation only in the case of UV radiation; during the application of ozone the pH level of the system did not have any influence on the degradation. Oxygen and synthetic air had the strongest effect on ozone degradation (comparable results); in the case of technical air the final dye concentration was higher up to 30 %. The gas flow of 1.5 dm3.min-1 was stated as optimal with the ozonizer output 30 W (maximal). At minimal power the ozonizer produced very low amount of ozone.

This Diploma thesis is focused on physical and chemical effects which contribute to the decomposition of organic dyes by diaphragm discharge generated in water solutions. Due to the application of DC high voltage source in continuous regime, there is an effect of electrolysis contributing to the dye decomposition by diaphragm discharge. The aim of this work was to find out when the electrolysis is running (or when is the moment of discharge breakdown) and which factors influence the breakdown. The other goal was decomposition of selected textile and food organic dyes by electrolysis itself. In the theoretical part, theory about creation of electrical discharges in aqueous solutions is noted and various types of underwater discharges are described. Background researches about underwater electrical discharges used in the world are mentioned as well as the use of diaphragm discharges and various ways how to remove organic dyes from wastewater. Finally, theories of electrolysis, UV-VIS spectroscopy and basis of other analytical methods useful for detection of organic molecules are described. Experimental part is oriented to experiment procedure which was carried out in a reactor with separated electrode areas. Separation was made by dielectric diaphragm with a pinhole in the centre. Its initial diameter was 0.4 mm. Used chemicals and course of experiments are described in this part, too. First, the breakdown moment in the reactor was investigated (i. e. determination, when only electrolysis was operating) by formation of hydrogen peroxide and measurement of dynamic (time resolved) electrical characteristics. Next, decomposition of selected dyes by electrolysis was carried out. As the decomposition was related to decolorization of the solution, UV-VIS spectroscopy in the range of 350–700 nm was used for determination of dye concentration. Next part focused on results presents various factors which had an effect on breakdown of diaphragm discharge. These factors are kind of used electrolyte, initial conductivity of solution, kind of dye, temperature of solution and type of reactor (or solution volume). From the result, the most important factor is initial solution conductivity. After the determination of the breakdown moment, the electrolysis of organic dyes was performed. The applied current was 10 mA, initial conductivity was 500 µS/cm and used electrolyte was NaCl. Moreover comparison of dye decomposition in dependence on the different applied power was realized. From this comparison one can assume, there is no significant contribution of electrolysis (the efficiency is approximately 15 %) to the diaphragm discharge in aqueous solution.