This thesis deals mainly with two oxidation reactions: water oxidation and aerobic oxidation, both of which have been applied in a biomimetic fashion. In the former reaction molecular oxygen is generated whereas in the latter it was used as terminal oxidant in oxidation reactions. The first part of this thesis describes the synthesis of different ruthenium and manganese complexes that could potentially act as catalysts for water oxidation. This part includes a discussion of the stability and reactivity of a new manganese(III) amide-type complex, that has been used as a catalyst for both epoxidation of stilbene and alcohol oxidation. The second part of this thesis discusses the synthesis of two new hybrid catalysts consisting of hydroquinone linked cobalt(II) salophen and cobalt(II) salmdpt, which have been used as oxygen-activating catalysts in aerobic oxidation reactions. The former catalyst was applied to the Pd-catalyzed reactions such as 1,4-diacetoxylation of cyclohexadiene whereas the latter was applied to the Ru-catalyzed oxidation of secondary alcohols to ketones. Moreover, these two hybrid catalysts could be used in the Pd-catalyzed carbocyclization of enallenes. In all cases molecular oxygen was used as the stoichiometric oxidant.

This thesis describes the host-guest chemistry between Cucurbit[7]uril (CB[7]) and CB[8] and a series of guests including bispyridinium cations, phenols and  napthalenes. These guests are bound to ruthenium polypyridine complexes or ruthenium based water oxidation catalysts (WOCs). The investigations are based upon utilizing the covalently linked photosensitizer and the electronic effects and chemical processes are investigated. / QC 20100927

Le but de la thèse est d'étudier l'influence de la microstructure des composites ZnO/TiO2 sur leurs propriétés dans la dégradation photocatalytique des polluants organiques et dans l'oxydation de l'eau photoassistée. Pour réaliser cette étude, nous avons choisi la conception basée sur des nano bâtonnets ZnO supportés sur une électrode de verre recouverte d'ITO (Indium Tin Oxide). Les nano bâtonnets de ZnO ont ensuite été recouverts d'une couche de TiO2 dans différentes conditions. La composition et la microstructure des composites ZnO(cœur)/TiO2(coquille) ont été modifiées dans le but d'élucider comment ces paramètres influencent leur activité photocatalytique. La couche TiO2 de morphologie différente (discontinue ou compacte) a été élaborée. Nous avons montré que le composite contenant la couche de TiO2 discontinue possède une activité plus élevée dans la dégradation de MB et dans l'oxydation de H2O sous 400 nm. Cette photoactivité améliorée a été attribuée à une meilleure accessibilité pour les réactifs de l'interface ZnO/TiO2 à travers la couche de TiO2. Aussi nous avons pu améliorer l'activité des composites sous la lumière visible. Dans ce but, les composites constitués de nano bâtonnets de ZnO supportés sur ITO ont été recouverts de TiO2 dopé à l'azote et décorés de nanoparticules d'or. Il a été trouvé que même une faible charge d'or (0,37% at.) permet une augmentation de 60% de la vitesse de décoloration photocatalytique du MB sous la lumière visible par rapport à l'échantillon sans or en raison de l'effet plasmonique. Un dopage simultané à l'azote et à l'or a permis également de multiplier par trois le photocourant dans l'oxydation photoassistée de l'eau. / The aim of the thesis is to study the influence of microstructure of ZnO/TiO2 composites on their properties in photocatalytic degradation of organic pollutants, and in photoassisted water oxidation. To realize such study we chose the design based on ZnO nanorods supported on ITO (Indium Tin Oxide)-coated glass electrode. The ZnO nanorods were then covered with a layer of TiO2 under different conditions. The composition and microstructure of the obtained ZnO(core)/TiO2(shell) composites were modified in the aim to elucidate how these parameters influence their photocatalytic activity. The results of studies lead to elaboration of two most distinctive variants of sol-gel procedure that allow to deposit TiO2 layers of controlled thicknesses and different morphology (rugged or compact). The composite containing the rugged TiO2 layer was shown to possess significantly higher activity in MB degradation and in photoassisted H2O oxidation under 400 nm. This improved photoactivity was attributed to a higher porosity and better accessibility of ZnO/TiO2 interface region through the rugged TiO2 layer by the reagents. The effort was also made to enhance the visible light activity of the composites. To this aim the composites consisting of ITO-supported ZnO nanorods covered with nitrogen-doped titanium dioxide and decorated with Au nanoparticles. It was found that even a low Au loading (0.37% at.) resulted in 60% enhancement of photocatalytic decolorization of MB under visible light with respect to the Au-free sample owing to plasmonic effects. A simultaneous N-doping and Au decoration allowed also to multiply by three the photocurrent in photoassited water oxidation.

La medición de efectos isotópicos es una herramienta importan­te en el estudio de las transformaciones químicas. El uso de efec­tos isotópicos de átomos ligeros como el deuterio es muy común e incluso aparece en muchos textos básicos de química. Lamen­tablemente, el uso de efectos isotópicos de átomos pesados no ha recibido la misma atención a pesar de su gran utilidad. Este manuscrito sirve como introducción a este tema importante. / The determination of isotope effects is an important tool in the study of chemical transformations. Very common in the liter­ature is the use of deuterium isotope effects, which is typically covered in many textbooks. Unfortunately, heavy atom isotope effects have not received the same attention despite its great rel­evance. This article will serve as an introduction to this very important topic.

abstract: Developing a system capable of using solar energy to drive the conversion of an abundant and available precursor to fuel would profoundly impact humanity's energy use and thereby the condition of the global ecosystem. Such is the goal of artificial photosynthesis: to convert water to hydrogen using solar radiation as the sole energy input and ideally do so with the use of low cost, abundant materials. Constructing photoelectrochemical cells incorporating photoanodes structurally reminiscent of those used in dye sensitized photovoltaic solar cells presents one approach to establishing an artificial photosynthetic system. The work presented herein describes the production, integration, and study of water oxidation catalysts, molecular dyes, and metal oxide based photoelectrodes carried out in the pursuit of developing solar water splitting systems. / Dissertation/Thesis / Ph.D. Chemistry 2013

No description available.

A sustainable solution for meeting the energy demands at our planet is by utilizing wind-, solar-, wave-, thermal-, biomass- and hydroelectric power. These renewable and CO2 emission-free energy sources are highly variable in terms of spatial and temporal availability over the Earth, introducing the need for an appropriate method of storing and carrying energy. Hydrogen has gained significant attention as an energy storage- and carrier media because of the high energy density that is exploited within the ‘power-to-gas’ process chain. A robust way of producing sustainable hydrogen is via electrochemical water splitting. In this work the search for new heterogeneous catalyst materials with the aim of increasing energy efficiency in water splitting has involved methods of both electrochemical water splitting and chemical water oxidation. Some 21 compounds including metal- oxides, oxofluorides, oxochlorides, hydroxide and metals have been evaluated as catalysts. Two of these were synthesized directly onto conductive backbones by hydrothermal methods. Dedicated electrochemical cells were constructed for appropriate analysis of reactions, with one cell simulating an upscale unit accounting for realistic large scale applications; in this cell gaseous products are quantified by use of mass spectrometry. Parameters such as real time faradaic efficiency, production of H2 and O2 in relation to power input or overpotentials, Tafel slopes, exchange current density and electrochemical active surface area as well as turnover numbers and turnover frequencies have been evaluated. Solubility, possible side reactions, the role of the oxidation state of catalytically active elements and the nature of the outermost active surface layer of the catalyst are discussed. It was concluded that metal oxides are less efficient than metal based catalysts, both in terms of energy efficiency and in terms of electrode preparation methods intended for long time operation. The most efficient material was Ni-Fe hydroxide electrodeposited onto Ni metal foam as conductive backbone. Among the other catalysts, Co3Sb4O6F6 was of particular interest because the compound incorporate a metalloid (Sb) and redox inert F and yet show pronounced catalytic performance. In addition, performance of materials in water splitting catalysis has been discussed on the basis of results from electron microscopy, solubility experiments and X-ray diffraction data.

Two series of new mononuclear ruthenium complexes with hydrophobic or hydrophilic ligands [Ru(bda)L2] and [Ru(pdc)L3] (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; H2pdc = 2,6-pyridinedicarboxylic acid; L = pyridyl ligands) were synthesized and their electrochemical properties and catalytic activity toward water oxidation were examined. It was revealed that the hydrophobic ligands introduced to [Ru(bda)L2 ] improved the catalytic performance, ahnost twofold TON and TOF values were achieved compared to the [Ru(bda)] catalyst with hydrophilic ligands. The cyclic voltammogram of [Ru(bda)L2] exhibited marginal difference between the catalysts with hydrophobic ligands and hydrophilic ones, implying that the hydrophobic ligands promoted the catalytic activity by :lacilitating formation of a reaction intermediate dimer.

This thesis concerns the development and the study of Iron-based water oxidation catalysts (WOCs) and how to immobilize them onto the hydrophobic surface of a carbon paste electrode. In the introductory chapter a general background of the field of water splitting and this thesis is given. In the second chapter, experimental performance is described from synthesis to measurements of a complete complex-doped electrode. The third chapter deals with the results and the discussion of the performed experiments. In chapter four, a descriptive conclusion of the obtained data is held. / Det här arbetet berör studien och utvecklingen utav järnbaserade katalysatorer, speciellt framtagna för för delning utav vatten. Utöver detta undersöks även om dessa katalysatorer (WOCs) kan immobiliseras på den hydrofoba ytan hos elektroder gjorda på kol-pasta. I det inledande kapitlet ges en generell bakgrund till området som berör delning utav vatten. I det andra kapitlet presenteras det experimentella utförandet utav synteser samt elektrokemiska mätningar som berörts under arbetets gång i jakten på en komplexdopad elektrod. I det tredje kapitlet diskuteras resultaten från mätningarna samt möjliga framtidsutsikter. I det fjärde kapitlet presenteras slutsatserna utav studien.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20337号 / 工博第4274号 / 新制||工||1662(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 田中 庸裕, 教授 梶 弘典, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM