Dans le contexte éco-environnemental actuel, l’Humanité est à la recherche d’alternatives pour remplacer les carburants fossiles responsables du changement climatique affectant le quotidien un peu plus chaque année. Inspiré par la Nature et le processus de la photosynthèse, un nouveau domaine à l’interface entre chimie, physique et ingénierie émergea dans les années 70 : la photosynthèse artificielle. Depuis, de nombreux systèmes catalytiques ont été rapportés mais leur intégration à l’échelle commerciale n’est pas encore d’actualité. De nombreux défis demeurent afin d’améliorer les performances, coupler les différentes réactions et s’assurer de la stabilité à long terme des dispositifs. Dans le cadre de cette thèse de doctorat, nous nous sommes attachés à explorer la chimie de coordination de complexes de ruthénium et de rhénium, omniprésents dans la littérature mais dont les propriétés peuvent être encore largement modulées par le design de nouveaux ligands. Dans un deuxième temps, les polyoxométallates, composés inorganiques à mi-chemin entre oxydes et molécules aux propriétés fascinantes, ont été recrutés pour développer des dyades covalentes, stratégie permettant de stabiliser un chromophore dans les conditions photocatalytiques. / In the current ecological and environmental context, Mankind needs to find alternative energy sources to replace fossil fuels, as their combustion is a major cause of the current global climate change affecting our daily life a bit more each year. Inspired by Nature and the photosynthetic process, a new area at the interface between chemistry, physics and engineering has emerged in the 70s: artificial photosynthesis. Since then, many catalytic systems have been reported but their integration at commercial scale has not yet been achieved. Several challenges remain to improve their performances, ensure efficient coupling between the different reactions and enhance the long-term stability of these devices. Within this doctoral thesis, we have focused on exploring the coordination chemistry of ruthenium and rhenium complexes, ubiquitous in the literature though their properties can still be vastly tuned by designing new ligands. In a different approach, polyoxometalates, which are inorganic compounds half-way between oxides and molecules with fascinating properties, were recruited to develop covalent dyads, a strategy enabling stabilization of the dye under photocatalytic conditions.

L'objectif de ce travail de thèse était de tester le textile lumineux en termes de performances photocatalytiques en milieu aqueux. La durabilité des textiles face à une exposition prolongée à une irradiation UVA a été testée. Les tests ont mis en évidence un problème de vieillissement des tissus enduits de TiO2, induisant l'apparition d'une inhomogénéité de l'émission de lumière sur la surface du textile. Un modèle mathématique a été développé afin d'exprimer et de prévoir ce vieillissement en fonction du temps d'exposition aux UVA. Le dépôt d'une couche protectrice de silice a permis de résoudre ce problème de vieillissement. Parallèlement, les textiles lumineux enduits de TiO2 ont été caractérisés. La localisation de SiO2 et TiO2 par MEBE et analyse EDX a été démontrée comme étant homogène sur la surface des fibres optiques, mise à part pour le dépôt de TiO2 P25 localise en amas. La quantité de photocatalyseur déposé sur les textiles ainsi que l'absorbance des dépôts ont été évaluées. L'étude de l'adhérence des dépôts a démontré la stabilité du TiO2. Enfin, les performances photocatalytiques des différents textiles enduits de photocatalyseur ont été testées sur la dégradation de deux polluants modèles, l'acide formique et le phenol, en réacteur ferme. L'étude de la vitesse de dégradation en fonction de la masse de TiO2 a permis de déterminer la masse optimum (environ 2mg cm-2). Des rendements photoniques de l'ordre de 30 à 55% dans le cas de l'acide formique et de 6 à 8% pour le phenol ont été obtenus. Un réacteur pilote plan, ouvert, a permis de confirmer les résultats obtenus et ouvre la voie à une configuration multicouche, en vue d'une application industrielle / The objective of this thesis was to test luminous textiles in terms of photocatalytic performances in aqueous medium. The durability of textile under long-time UVA irradiation was tested. Results showed the aging of luminous textile coated by TiO2, involving an inhomogeneity of light emission on the overall surface of the textile. A mathematical model was developed to express and predict the aging depending on the time of exposure to UVA. Also, a protective layer of silica allows avoiding the optical fiber aging. In parallel, luminous textiles coated by TiO2 were characterized. The location of SiO2 and TiO2 by ESEM and EDX analysis was shown to be uniform over the surface of optical fibers textiles, except for TiO2 P25 coating, located in clusters. The amount of photocatalyst deposited on the textiles, and the absorbance of the coatings were determined. Moreover, the study of coating adhesion demonstrated excellent adhesion and stability of the photocatalyst layer. Finally, the photocatalytic performances of the different TiO2 coatings were tested for degradation of two model pollutants, formic acid and phenol, in batch reactor. The study of the evolution of the degradation rate with the mass of photocatalyst was used to determine the optimum mass of TiO2 (about 2mg cm-2). Photonic yields ranging from 30 to 55% in the case of formic acid and 6 to 8% in the case of phenol were obtained. A continuous plan pilot reactor confirmed the results and opens the way for a multi-layer configuration, for industrial application

Inorganic colloidal synthesis, without a doubt, lies at the foundation of many contemporary areas of nanoscience and nanotechnology. At the advent of the 21st century, much progress has been made in the size, shape / morphological control and surface engineering of metal oxides resulting in a diverse library of macroscopic crystal architectures with well-defined surface properties. In this thesis, we start by introducing the self-assembly of the iron(oxy-, hydro-)xide while briefly reviewing some fundamental concepts of solid-state chemistry. Specific information on the family of iron oxide and iron(oxy-, hydro-)xide, as relevant to crystalline phase control, has been highlighted to direct our discussion of the synthesis of diverse crystal morphologies. Furthermore, we briefly underline and discuss the kinetic and thermodynamic control of colloidal crystal morphologies through reasonably established knowledge of anisotropic growth rates in the perspective of iron oxides' facets or crystalline planes. Lastly, we review the state-of-the-art wet chemical synthetic approaches, while using different iron(oxy-, hydro-)xide crystals as examples, for the purpose of explaining our synthetic work of choice. The main work of this thesis is entirely focused on the "facile synthesis and fine morphological tuning of branched hematite (??-Fe2O3) crystals for photodegradation of azo-type dyes".. We would discuss the crucial parameters for fine morphological tuning in the context of controlling the anisotropic growth rates of branched ??-Fe2O3 crystals instead of phase transformation. In our work, we have significantly improved the synthesis of dendritic "feather-like" and "starfish-like" for their size reduced variants for use in photocatalysis.

Organische Schadstoffe werden in vielen Phasen unseres täglichen Lebens in den Wasserkreislauf eingeleitet. Die herkömmliche Abwasserbehandlung ist nicht zur effektiven Entfernung einiger dieser Stoffe, insbesondere von Arzneimitteln, geeignet. Die Fotokatalyse basierend auf der Suspension von katalytischen Nanopartikeln und ultraviolettem Licht stellt eine effiziente Methode dar, um diese organischen Stoffe im Abwasser zu reduzieren. Während das allgemeine Konzept der fotokatalytischen Wasserreinigung gut etabliert ist, fehlte ein beschreibendes und einfach anwendbares Modell der wesentlichen Abbauprozesse. Ein solches Modell ist entscheidend, um experimentelle Ergebnisse systematisch vergleichen zu können, und stellt eine wertvolle Hilfe bei der Optimierung von Prozessen dar. Diese Arbeit präsentiert einen Modellierungsansatz zur Simulation der kinetischen Prozesse basierend auf dem Langmuir-Hinshelwood-Mechanismus. Dieses Grundmodell wurde erweitert, um auch die Bildung von organischen Zwischenprodukten zu beschreiben. Diese Erweiterungen basieren entweder auf einem inkrementellen oder einen fragmentierenden Abbaumechanismus, der durch das Einbinden von überschüssigen Bindungen ergänzt werden kann. Die simulierte Konzentrationsentwicklung von Zwischenprodukten sowie die Entwicklung des verbleibenden organischen Kohlenstoffes werden für verschiedene Modellannahmen bezüglich ihrer Desorptionsraten von der Photokatalysatoroberfläche diskutiert. Die Modellparameter wurden aus dem Vergleich mit experimentellen Ergebnissen ermittelt. Grundlegende Experimente wurden unter Verwendung des Antibiotikums Ciprofloxacin und des Farbstoffs Methylenblau als Beispiele für organische Verbindungen und Titandioxid und Zinkoxid als fotokatalytische Materialien durchgeführt. Darüber hinaus wird die Anwendbarkeit des Modells auf komplexere Systeme durch den Vergleich mit dem fotokatalytischen Abbau von 14 Medikamenten im Abfluss von Kläranlagen demonstriert. Nach der Evaluierung des Modells wurde es in ein Open-Source-Softwarepaket implementiert, um eine breitere Anwendung zu ermöglichen und eine solide Grundlage für weitergehende Entwicklungen zu schaffen.:Abstract Kurzfassung Symbols Constants Abbreviations 1. Motivation 2. Introduction 2.1. Modeling and simulation 2.2. Heterogeneous photocatalysis 2.2.1. History 2.2.2. Semiconductor band structure 2.2.3. Interface between a semiconductor and a redox electrolyte 2.3. Photocatalytic material 2.3.1. Overview 2.3.2. Titanium dioxide 2.3.3. Zinc oxide 2.4. Light sources 2.4.1. Solar 2.4.2. Fluorescent tubes and mercury-vapor lamps 2.4.3. Light-emitting diodes 2.4.4. Organic light-emitting diodes 3. Materials and methods 3.1. Analytic methods 3.1.1. Nanoparticle characterization 3.1.2. Ultraviolet-visible absorption spectrometry 3.1.3. SPE-HPLC-MS/MS 3.1.4. Non-purgeable organic carbon 3.2. Experimental investigations 3.2.1. Model substances 3.2.2. Adsorption-desorption 3.2.3. Photocatalytic degradation 3.2.4. Wastewater treatment plant effluent 3.3. Modeling approach 3.3.1. Single organic species model 3.3.2. Multiple organic species model 3.4. Model implementation 3.4.1. Development objectives 3.4.2. Molecule parameters 3.4.3. Solving the differential equation system 3.4.4. Fit to experimental results 3.4.5. Availability 4. Results and discussion 4.1. Nanoparticle properties 4.2. Adsorption-desorption 4.3. Photocatalytic degradation 4.3.1. Single organic species model 4.3.2. Multi organic species model 4.4. Wastewater treatment plant effluent 4.4.1. Influence of effluent 4.4.2. Degradation of pharmaceuticals in the effluent 5. Conclusions Appendix A. Analytical solution B. Effluent pharmaceuticals concentrations C. pdom handbook List of figures List of tables Bibliography / Organic pollutants are discharged into the water cycle at many stages in our daily lives. Conventional wastewater treatments are ineffective in the removal of some of them, especially clearing pharmaceuticals. Photocatalytic degradation utilizing catalytic nanosuspensions under ultraviolet irradiation represents an efficient method to reduce those organic components in the wastewater. While the general concept of photocatalytic water purification is well established, a descriptive and easy to use model of the essential processes was missing. Such a model is critical to ensure the systematic comparability of experimental results and supports process optimization. This work presents a modeling approach to simulate the involved kinetic processes based on the Langmuir–Hinshelwood mechanism. Further, the fundamental model is extended to include the formation of intermediate organic components. This extension uses either an incremental degradation mechanism or a fragmentation based mechanism, that can include excess bonds. The simulated concentration evolution of intermediates, as well as the evolution of the total organic carbon, are discussed for different model assumptions concerning their desorption rates from the photocatalyst surface. The model parameters were estimated from comparison with experimental findings. Basic experiments were performed using the antibiotic ciprofloxacin, and the dye methylene blue as organic compounds and titanium dioxid and zinc oxide as photocatalytic materials. Furthermore, the application of the model to more complex systems is shown by the photocatalytic degradation of 14 pharmaceuticals in wastewater treatment plant effluent. Following successful evaluation of this model, it was implemented in an open-source software package to enable a wider adoption and a sound foundation for further developments.:Abstract Kurzfassung Symbols Constants Abbreviations 1. Motivation 2. Introduction 2.1. Modeling and simulation 2.2. Heterogeneous photocatalysis 2.2.1. History 2.2.2. Semiconductor band structure 2.2.3. Interface between a semiconductor and a redox electrolyte 2.3. Photocatalytic material 2.3.1. Overview 2.3.2. Titanium dioxide 2.3.3. Zinc oxide 2.4. Light sources 2.4.1. Solar 2.4.2. Fluorescent tubes and mercury-vapor lamps 2.4.3. Light-emitting diodes 2.4.4. Organic light-emitting diodes 3. Materials and methods 3.1. Analytic methods 3.1.1. Nanoparticle characterization 3.1.2. Ultraviolet-visible absorption spectrometry 3.1.3. SPE-HPLC-MS/MS 3.1.4. Non-purgeable organic carbon 3.2. Experimental investigations 3.2.1. Model substances 3.2.2. Adsorption-desorption 3.2.3. Photocatalytic degradation 3.2.4. Wastewater treatment plant effluent 3.3. Modeling approach 3.3.1. Single organic species model 3.3.2. Multiple organic species model 3.4. Model implementation 3.4.1. Development objectives 3.4.2. Molecule parameters 3.4.3. Solving the differential equation system 3.4.4. Fit to experimental results 3.4.5. Availability 4. Results and discussion 4.1. Nanoparticle properties 4.2. Adsorption-desorption 4.3. Photocatalytic degradation 4.3.1. Single organic species model 4.3.2. Multi organic species model 4.4. Wastewater treatment plant effluent 4.4.1. Influence of effluent 4.4.2. Degradation of pharmaceuticals in the effluent 5. Conclusions Appendix A. Analytical solution B. Effluent pharmaceuticals concentrations C. pdom handbook List of figures List of tables Bibliography

Schwerpunkt der vorliegenden Arbeit war die Erstellung, Anpassung und Anwendung einer Methode, die es über die Quantifizierung gebildeter OH-Radikale ermöglicht, sowohl den Einfluss verschiedener Materialmodifikationen (physikalisch dotierte Nanokatalysatoren bzw. Biokompositmaterialien) als auch die Auswirkungen von Matrixbestandteilen oder hydrochemischen Randbedingungen auf die photokatalytische Effizienz der Materialien zu untersuchen. Zudem wurde angestrebt, dass sich die Anwendbarkeit der Methode nicht nur auf die Photokatalyse beschränkt, sondern auch auf andere AOPs ausgeweitet werden kann. Des Weiteren wurde über die Umsetzung der Modellspurenstoffe Carbamazepin und Diclofenac die Wirksamkeit der Katalysatormaterialien untersucht. Anhand von Versuchen im Labormaßstab werden unter Anwendung der entsprechenden Methode zur Quantifizierung der OH-Radikale bisherige zugrundeliegende Hypothesen zur photokatalytischen Erzeugung von OH-Radikalen (Einfluss von pH und Oberfläche) überprüft und modifiziert. Dabei werden neue Ansätze zur Oberflächenabhängigkeit der OH-Radikalbildung in AOPs (EAOP Diamantelektrode, UV/VUV), die Effizienz von UV/VUV im Vergleich zu UVA-Photokatalyse, die Anwendung von S-Layer-Proteinen in photokatalytischen Biokompositmaterialien sowie eine photokatalytische Umsetzung von Carbamazepin unter Nutzung neuartiger Katalysatoren und Sonnenlicht untersucht. Mit Hilfe der gewonnenen Erkenntnisse ist es möglich, photokatalytisch aktive Materialien über die OH-Radikalbildungskapazität, als Basisprozess einer photokatalytischen Eliminierung von pharmazeutischen Wirkstoffen aus Wässern, mit Hinblick auf ihre Effizienz und Haltbarkeit zu untersuchen. Daneben bietet das erstellte Konzept zur analytischen Anwendung der OH-Radikalbestimmung neben der Gelegenheit für interessante Vergleiche diverser AOP-Systeme auch die Möglichkeit einer Charakterisierung und Optimierung der einzelnen AOPs. Zudem konnte gezeigt werden, dass die Anwendung von nano-Biokompositmaterialien unter Verwendung von S-Layer-Protein zur Herstellung multifunktionaler photokatalytischer Beschichtungen vielversprechend ist. Die Ergebnisse der Arbeit unterstreichen, dass die analytische Erfassung von Transformationsprodukten aus photokatalytischen bzw. oxidativen Umsetzungen im Allgemeinen von großer Bedeutung ist, jedoch allein nicht ausreicht, um hinreichend sichere Aussagen über eine mögliche Gefährdung für Mensch bzw. Ökosystem zu erhalten. / The current work was focused on the preparation, adaption and application of an analytical method for the determination of OH radicals for the comparison of the activity of different photocatalytic materials in relation to the material modification (i.e. physically doped nanomaterials or biocomposite materials) and the composition of the water matrix. Furthermore, the application of the OH radical assay should be extended on other AOPs. The degradation of the model compounds carbamazepine and diclofenac was examined to determine the efficiency of the novel photocatalysts. By using appropriate OH radical assays in laboratory scale experiments, present hypotheses in relation to the photocatalytic formation of OH radicals (i.e. influence of pH or surface) were examined and modified. New approaches on the formation of OH radicals with respect to the surface within AOPs (EAOP diamond electrodes or UV/VUV), the efficiency of UV/VUV in relation to photocatalysis using UVA irradiation, the application of S-layer proteins in biocomposite materials and the photocatalytic degradation of carbamazepine applying novel photocatalysts and natural sunlight were examined. Based upon the findings, it was possible to compare photocatalytic materials regarding efficiency and stability by means of the capacity to form OH radicals as the base process for the oxidative degradation of pharmaceutical trace compounds. The analytical concept offers the possibility to compare different AOPs and to characterize or optimize a single AOP. Furthermore, it was shown that the implementation of nanoscale biocomposite materials using S-layer proteins for the preparation of multi-functional coatings for photocatalytic applications is promising. In addition, the current work confirmed that the examination of transformation products of photocatalytic treatment processes or other oxidative reactions is very important. However, the analytical characterization alone is not sufficient to predict potential hazards to human health or the ecosystem with adequate reliability.

No description available.

Contamination of surface and ground water from industrial wastes and anthropogenic activities represents one of the greatest challenges to the sustainable development of human society. Heterogeneous photocatalysis, a kind of advanced oxidation process characterized by the production of highly oxidative hydroxyl radicals, is a relatively novel subject with tremendous potential in water treatment applications.     The purpose of this research was first to develop feasible hydroxyl radical detection methods, which can be used to evaluate efficiency of photocatalytic process, and second to prepare immobilized TiO2 films with high photocatalytic activities by the sol gel method.     The feasibility of Indigo carmine and phthalic hydrazide as OH-radical probes was investigated. The organic dye Indigo carmine absorbs visual light strongly at 610 nm and its destruction can be monitored conveniently in a spectrophotometer. Results showed that both ·OH and HO2· can bleach Indigo carmine, and the bleaching yield of ·OH was pH independent. The photocatalytic dye bleaching in black light UV illuminated Degussa P25 TiO2 aerated suspensions was then investigated. A strong pH dependency of the bleaching yield was found.  This implies that the quantum yield of OH radical at pH 3 is one fourth compared to that at pH 10. The reaction of the OH radical with phthalic hydrazide will form strongly chemiluminescent 3-hydroxyphthalic hydrazide. Using the more specific phthalic hydrazide as OH radical probe, an even stronger pH dependent quantum yield of OH radical was found. At pH 10 the quantum yield reached the same magnitude as that obtained by using Indigo carmine, whereas the quantum yields at acidic pH were close to zero. However it was found that the addition of phosphate and fluoride anions can substantially enhance the OH radical yield at acidic pH by blocking the adsorption of phthalic hydrazide onto the TiO2 surfaces. Hence the adsorption of phthalic hydrazide to TiO2 is an important factor to consider when this method is used.     Photocatalytic TiO2 films coated on metal plates were prepared by a sol gel method using titanium isopropoxide as TiO2 precursor and isopropanol as solvent. The photocatalytic activity of the obtained films was evaluated by bleaching of indigo carmine at pH 9 under black light UV irradiation. The effect of the molar ratio of isopropanol, water and hydrochloric acid to titanium isopropoxide was studied. It was also shown that the activities of TiO2 films are considerably influenced by calcination temperature, coating cycles and the supporting materials. / Förorening av yt- och grundvatten från industrier och humana aktiviteter utgör en av de största utmaningarna för en hållbar utveckling av det mänskliga samhället. Heterogen fotokatalys, en slags avancerad oxidations process som kännetecknas av att starkt oxidativa hydroxylradikaler produceras, är en relativt ny teknik med stor potential för vattenrening.     Ett syfte med detta licentiatarbete var först att utveckla och genomföra olika metoder för att detektera bildningen av hydroxylradikaler såväl i laboratoriet som i tekniska miljöer. Det andra syftet med arbetet var att syntetisera immobiliserade TiO2 filmer med hög fotokatalytisk effektivitet med en sol-gel metod.     Möjligheten att använda indigokarmin och ftalhydrazid som OH-radikalprob undersöktes. Det organiska färgämnet indigokarmin absorberar synligt ljus starkt vid 610 nm vilket gör att dess nedbrytning lätt kan följas i en spektrofotometer. Resultaten av gammaradiolys visade att båda •OH och HO2• kan bleka indigokarmin och att den blekning som härrör från •OH var oberoende av pH. Fotokatalytisk blekning av indigokarmin med blacklight UV bestrålning av  Degussa P25 TiO2 suspensioner undersöktes sedan. Ett starkt pH-beroende av blekningsutbytet erhölls vilket tolkas som att kvantutbytet av OH-radikaler vid pH 3 är en fjärdedel jämfört med det vid pH 10.     När ftalhydrazid reagerar med OH-radikaler bildas starkt kemiluminiscent 3-hydroxy-ftalhydrazid. Med denna  specifika OH-radikalprob, erhölls ett ännu starkare pH beroende. Vid pH 10 var kvantutbytet i paritet med det som erhölls med indigokarmin, medan kvantutbytet vid lågt pH var nära noll. Tillsats av fosfat-  och fluoridjoner visade sig avsevärt öka OH-radikalutbytet vid lågt pH-värde genom att blockera adsorption av ftalhydrazid på TiO2 ytorna. Adsorptionen av ftalhydrazid på TiO2 är således en viktig faktor när denna metod används.     Fotokatalytiskt verksamma TiO2-filmer på metallplattor framställdes med sol-gel metoden med titan-isopropoxide som TiO2-prekursor och isopropanol som lösningsmedel. Den fotokatalytiska aktiviteten av TiO2-belagda plattor utvärderades genom blekning av indigokarmin vid pH 9 under blacklight UV-bestrålning. Effekten av olika proportioner mellan isopropanol, vatten och saltsyra till titan isopropoxide undersöktes. Det visade sig att denfotokatalytiska aktiviteten av TiO2-plattorna i hög grad påverkades av kalcineringstemperatur, beläggningscykler och materialet i plattorna.

High power impulse magnetron sputtering has shown a lot of promise as a way of depositing photocatalytic thin films of titanium dioxide at low temperatures, however, the films deposited are often amorphous and display uncertain photocatalytic abilities. This thesis explores the deposition and characterization of photocatalytic thin films deposited with high power impulse magnetron sputtering.  Multiple films were deposited with reactive sputtering in both the oxide and metal mode of operations at different temperatures, duty cycles and substrate biases. The crystal structure, microstructure and photocatalytic activity of the samples were then characterized in order to correlate to each other as well as the growth conditions. Crystallinities were determined via a combined use of gracing incidence x-ray diffraction and Raman spectroscopy, microstructures were explored in cross-sectional images taken using scanning electron microscopy and the photocatalytic ability was measured by quantifying the rate constant during degradation of stearic acid while under UV-illumination.  It was found that the crystal structure of the sputtered films was influenced by the deposition mode used: oxide mode depositions yielded an anatase structure while metal mode depositions resulted in rutile or mixed structures. The only crystalline films were formed with substrate heating, the application of bias was found to correlate with the formation of more rutile and the most crystalline films were deposited with a higher duty cycle.  Photocatalytic films were successfully deposited at room temperature, even though they were amorphous. Interestingly, the anatase samples were not found to be the most reactive, instead it was found that the crystal structure only displayed a weak correlation to the reactivity of the films. The findings in this work suggest that the reactivity was also heavily influenced by the surface roughness of the samples as well as their microstructures.

abstract: Continuing and increasing reliance on fossil fuels to satisfy our population’s energy demands has encouraged the search for renewable carbon-free and carbon-neutral sources, such as hydrogen gas or CO2 reduction products. Inspired by nature, one of the objectives of this dissertation was to develop protein-based strategies that can be applied in the production of green fuels. The first project of this dissertation aimed at developing a controllable strategy to incorporate domains with different functions (e. g. catalytic sites, electron transfer modules, light absorbing subunits) into a single multicomponent system. This was accomplished through the rational design of 2,2’-bipyridine modified dimeric peptides that allowed their metal-directed oligomerization by forming tris(bipyridine) complexes, thus resulting in the formation of a hexameric assembly. Additionally, two different approaches to incorporate non-natural organometallic catalysts into protein matrix are discussed. First, cobalt protoporphyrin IX was incorporated into cytochrome b562 to produce a water-soluble proton and CO2 reduction catalyst that is active upon irradiation in the presence of a photosensitizer. The effect of the porphyrin axial ligands provided by the protein environment has been investigated by introducing mutations into the native scaffold, indicating that catalytic activity of proton reduction is dependent on axial coordination to the porphyrin. It is also shown that effects of the protein environment are not directly transferred when applied to other reactions, such as CO2 reduction. Inspired by the active site of [FeFe]-hydrogenases, the second approach is based on the stereoselective preparation of a novel amino acid bearing a 1,2-benzenedithiol side chain. This moiety can serve as an anchoring point for the introduction of metal complexes into protein matrices. By doing so, this strategy enables the study of protein interactions with non-natural cofactors and the effects that it may have on catalysis. The work developed herein lays a foundation for furthering the study of the use of proteins as suitable environments for tuning the activity of organometallic catalysts in aqueous conditions, and interfacing these systems with other supporting units into supramolecular assemblies. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019

Hydrothermal synthesis is one of the most widely used methods for preparing nanoparticles of titanium dioxide. The process carried out at elevated temperatures and pressure, which facilitates the transformation of amorphous to crystalline titanium dioxide. Change of reaction conditions of the process (reactants concentration, temperature, time, pH, etc.) leads to change in morphology, microstructure and crystallinity of titanium dioxide nanoparticles. In this work the method of titanium dioxide preparation is briefly described. The titanium dioxide was prepared from a precursor titanium oxochloride and potassium hydroxide as the precipitating agent. Thus prepared titanium dioxide was immobilized on a glass substrate by material printing. This is a modern, highly precise and contactless method for preparing thin films. The photocatalytic activity of printed thin films of titanium dioxide was investigated by degradation of 2,6-dichlorindophenol at different irradiance. It was found that the sample prepared by hydrothermal treatment at 160 °C shows very similar photocatalytic activity to Degussa P25.