Selektivität zu erreichen ist eines der Hauptziele der Chemie. In der Katalyse wird allgemein von einem engen Zusammenhang zwischen der Selektivität und der Katalysatorstruktur ausgegangen - allerdings erschwert die komplexe mikroskopische Struktur realer Katalysatoren ein tiefergehendes Verständnis; daher wird versucht, weitergehende Erkenntnisse an strukturell vereinfachten Materialien zu gewinnen. Für diese Arbeit wurde hierzu ein Pd/Fe3O4-Modellkatalysator verwendet. Auf diesem System wurde die Selektivität in zwei katalytische Modellreaktionen untersucht. Die Reaktantenexposition erfolgte dabei über Molekularstrahlen im Hochvakuum, und die Reaktionsraten wurden massenspektrometrisch gemessen; Adsorbate wurden IR-spektroskopisch detektiert. - Zersetzung von Methanol: Es wird gezeigt, dass Methanol auf dem Oxid Fe3O4 sehr selektiv durch Reaktion mit Oberflächensauerstoff (Mars-van-Krevelen-Mechanismus) zu Formaldehyd und Wasser dehydrogeniert wird. Auf Pd-Metall zersetzt sich Methanol im wesentlichen sehr schnell zu Kohlenstoffmonoxid und Wasserstoff (bzw. zu Kohlenstoffablagerungen in einer Nebenreaktion). Es werden Experimente gezeigt, die darauf hindeuten, dass Diffusion von oxidgebundenem Methanol/Methoxy auf die Pd-Metallpartikel signifikant zur Gesamtaktivität des Modellkatalysators beiträgt. - Umsetzung von 2-Buten mit Deuterium: Zunächst wird gezeigt, dass die Erzielung katalytischer Aktivität kritisch von der dissoziativen Adsorption des Reaktanden Deuterium abhängt, die durch Kohlenwasserstoffadsorbate stark inhibiert wird; es war allerdings möglich, diese Limitierung experimentell zu umgehen. Darüberhinaus wird gezeigt, dass die Hydrierungsreaktion durch die Anwesenheit stark zersetzter Kohlenwasserstoffablagerungen selektiv induziert werden kann, während die alternative Reaktion (H/D-Austausch/Isomerisierung) auch in Abwesenheit dieser Spezies abläuft; mögliche Erklärungsmodelle werden diskutiert. Schließlich wird die mögliche Ursache für die unter bestimmten Reaktionsbedingungen beobachteten unterschiedlichen Reaktionsraten mit cis- und trans-2-Buten als Reaktanten diskutiert. / The achievement of selectivity is one of the main objectives in chemistry. For catalysis, selectivity is generally seen to be closely linked with catalyst structure; the complex microscopic structure of real catalysts, however, obstructs to obtain a deeper understanding; for this reason, structurally simplified materials are studied. For the current work, studies have been conducted on a Pd/Fe3O4 model catayst. On this system, the selectivity in two catalytic reactions has been examined. The exposure of the reactants was effected by molecular beams in high vacuum, and the reaction rates have been measured mass spectrometrically; additionally, adsorbates were detected by IR-spectroscopy. - Decomposition of Methanol: It is shown that on the oxide Fe3O4 methanol is dehydrogenated very selectively to formaldehyde and water by reaction with surface oxygen of the oxide (Mars-van-Krevelen mechanism). On Pd metal it is mainly decomposed very quickly to carbon monoxide and hydrogen (and, in a side reaction, to carbonaceous deposits). Experiments are shown indicating that the diffusion of oxide-related methanol and methoxy to the Pd metal-particles contributes significantly to the overall activity of the model catalyst. - Conversion of 2-Butene with Deuterium: At first it is shown that the catalytic activity depends critically on the dissociative adsorption of the reactant deuterium, which is strongly inhibited by hydrocarbon adsorbates; it was, however, possible to overcome this limitation experimentally. In addition, it is shown that the hydrogenation reaction can be selectively induced in the presence of strongly dehydrogenated carbonaceous deposits, whereas the alternative reaction (H/D-exchange/isomerisation) can proceed also without the presence of those species; possible models for explanation are discussed. Finally, the possible origin of the different reaction rates with cis- and trans-2-butene that were observed only under certain reaction conditions is discussed.

Carbon supported PtNi nanoparticles were prepared by hydrazine reduction of Pt and Ni precursor salts under different conditions, namely by conventional heating (PtNi-1), by prolonged reaction at room temperature (PtNi-2) and by microwave assisted reduction (PtNi-3). The nanocomposites were characterized by XRD, EDX, XPS and TEM and used as electrocatalysts in direct methanol fuel cell (DMFC) reactions. Investigations into the mechanism of PtNi nanoparticle formation revealed that platinum nanoparticle seeding was essential for the formation of the bimetallic nanoparticles. The average particle size of PtNi prepared by microwave irradiation was the lowest, in the range of 2.9 – 5.8 nm. The relative rates of electrooxidation of methanol at room temperature as measured by cyclic voltammetry showed an inverse relationship between catalytic activity and particle size in the following order PtNi-1 < PtNi-2 < PtNi-3. / Singapore-MIT Alliance (SMA)

Direct Methanol Fuel Cells (DMFCs) are a promising source of energy due to their potentially high energy density, facilitated fuel delivery and storage, and precluded fuel processing. However, DMFCs have several challenges which need to be resolved before they can replace existing energy sources. Some of the challenges include lower power density, relatively high cost, and uncertain reliability. These issues are all promoted, at least in part, by the methanol crossover phenomenon, wherein membrane permeability allows the undesirable species transport of methanol from anode to cathode. This phenomenon also causes the requirement of dilute fuel mixtures, which is undesirable from an energy density viewpoint. Steady flow polarization curves were first analyzed at various concentrations. An optimal concentration range was found wherein both methanol crossover and concentration losses were effectively minimized. During the study of transient phenomena, the fuel was first temporarily discontinued. It was found that a significant cell potential enhancement occurred due to anodic fuel concentration reduction and thus depleting the reactant crossover. The percentage voltage increase was considerably greater at higher concentrations. Based on the fuel discontinuation, a hydraulic pulsing operation was developed and tested. During some of these continuous pulsing schemes, fuel discontinuation did not result in an instantaneous cell potential enhancement mainly due to the internal inertia of the membrane. Nonetheless, a significant cell potential and fuel efficiency enhancement was observed. In addition, the pulse of both fuel and current density resulted in a significant power density increase.

Due to overconsumption, fossil reserves are rapidly being depleted and various sources predict that they will not last until the end of 21st century. Moreover, the increase in the rate of global warming and the polluting matter emitted by the vehicles consuming fossil fuels has increased the search for renewable and clean energy sources. Alcohols and ethers, which contain fewer pollutants and have better burning properties, are commonly thought among clean fuel alternatives. Among the potential clean energy sources, dimethyl-ether is already in use in the automotive industries of many countries such as China and Japan, due to its low NOx and CO2 emissions, high cetane rating and efficient combustion characteristics, especially in diesel engines. In this work, dimethyl-ether synthesis is achieved using methanol dehydration reaction over solid acid catalysts. For this purpose, three different mesoporous MCM-41 type aluminum silicates have been synthesized with direct hydrothermal synthesis method and aluminum is added to the synthesized SBA-15 catalyst using impregnation method. Apart from the catalysts synthesized, different commercial catalysts such as aluminum oxide in different forms (&amp / #945 / and &amp / #947 / ), Nafion NR-50 and Nafion SAC-13 have also been tested in this reaction. These materials were characterized by methods such as XRD, EDS, SEM, and N2 physical adsorption and DRIFTS were also investigated in terms of paramters such as the conversion of methanol to products, selectivity and yield. The analyses have shown that AlSi1 is the most active of all the aluminum silicates synthesized in both 0.136 and 0.27 s.g/cm3 space times, with up to 80% methanol conversion in all temperatures tested. AlSi1 also has low by-product formation and similar to other aluminum silicates, its dimethyl-ether selectivity approaches 1 at 4000C. Among all synthesized catalysts, the dimethyl-ether yield was seen to be the highest for Al-SBA-15, which approaches 0.5 at 4000C for both space times. For all aluminum silicates synthesized, about 40% dimethyl-ether yield was obtained at the same temperature and space times. Among the aluminum oxides, &amp / #945 / -alumina was seen to be superior to others in &amp / #947 / forms in terms of conversion selectivity and yield, especially at low temperatures. As to Nafion catalysts, due to its much higher surface area and high Bronsted acidity, Nafion SAC-13 has shown higher activity compared to Nafion NR-50 for all temperatures and space times tested.

Our country continues to demand clean renewable energy to meet the growing energy needs of our time. Thus, natural gas, which is 87% by volume of methane, has become a hot topic of discussion because it is a clean burning fuel. However, the transportation of methane is not easy because it is a gas at standard temperature and pressure. The usage of transition metals for the conversion of small organic species like methane into a liquid has been a longstanding practice in stoichiometric chemistry. Nonetheless, the current two-step process takes place at a high temperature and pressure for the conversion of methane and steam to methanol via CO + H2 (syngas). The direct oxidation of methane (CH4) into methanol (CH3OH) via homogeneous catalysis is of interest if the system can operate at standard pressure and a temperature less than 250 C. Methane is an inert gas due to the high C-H bond dissociation energy (BDE) of 105 kcal/mol. This dissertation discusses a series of computational investigations of oxy-insertion pathways to understand the essential chemistry behind the functionalization of methane via the use of homogeneous transition metal catalysis. The methane to methanol (MTM) catalytic cycle is made up of two key steps: (1) C-H activation by a metal-methoxy complex, (2) the insertion of oxygen into the metal−methyl bond (oxy-insertion). While, the first step (C-H activation) has been well studied, the second step has been less studied. Thus, this dissertation focuses on oxy-insertion via a two-step mechanism, oxygen-atom transfer (OAT) and methyl migration, utilizing transition metal complexes known to activate small organic species (e.g., PtII and PdII complexes). This research seeks to guide experimental investigations, and probe the role that metal charge and coordination number play.

The production of methanol by use of water electrolysis and hydrogenation of carbon dioxide (Power-to-Methanol) is a promising pathway to reduce greenhouse gas emissions. The concept of process intensification and the associated utilization of an in-situ coupling of methanol synthesis with proton-conducting Solid Oxide Electrolysis Cells (H+-SOEC) is a possible way to increase the energy efficiency of this process. Based on an extensive literature research, a novel Power-to-Methanol reactor concept for a concentric in-situ-integration of a tubular H+-SOEC has been designed, manufactured and operated at the Chair of Hydrogen and Nuclear Energy at the Technische Universität Dresden. The conducted experiments served as reference points for the process simulations performed in the second part of this thesis. Here, the Power-to-Methanol process has been modelled and simulated by means of process systems engineering methods to evaluate the in-situ-process in comparison to an conventional uncoupled set-up based on planar H+-SOECs. For this task, a novel and firm H+-SOEC process model was developed and implemented. In addition, the heat integration potential and profitability of the two Power-to-Methanol concepts have been investigated by Pinch Point and Techno-Economic Analysis. On the experimental side, a proof-of-concept of the novel reactor design was demonstrated, but limitations regarding the optimal thermal profile and operational flexibility of each process were identified. Furthermore, the methanol production rate showed potential for further improvement. The simulation results have helped to understand the process characteristics and to locate optimal operation points regarding current density, temperature and pressure. In an optimised operation scenario, high energy efficiencies for both tubular in-situ and planar set-ups have been achieved, by means of harnessing the heat integration potential through exothermic H+-SOEC operation. Notwithstanding the above, planar set-ups have demonstrated to be substantially more profitable than tubular systems. This has been the first investigation on Power-to-Methanol processes based on H+-SOEC. The present work helps to identify remaining development objectives for the use of H+-SOEC and Power-to-Methanol processes in general. The results from experiments and simulations indicate the challenging utilization of tubular electrolysis cells, but also revealed new research priorities that should be addressed in the future.

No description available.

Pichia pastoris, a methylotrophic yeast is widely used for recombinant protein production. It has a well characterized methanol utilization (MUT) pathway, the enzymes of which are induced when cells are cultured in the presence of methanol. In this study, we have identified an unannotated zinc finger protein, which was subsequently named ROP (repressor of phosphoenolpyruvate carboxykinase, PEPCK) and characterized its function. ROP expression is induced in P. pastoris cells cultured in biotin depleted glucose ammonium medium as well as a medium containing methanol as the sole source of carbon. In glucose-abundant, biotin depleted cultures, ROP induces the expression of a number of genes including that encoding PEPCK. Interestingly, a strain in which the gene encoding ROP is deleted (ΔROP) exhibits biotin-independent growth. Based on a number of studies, it was proposed that the ability of ΔROP to grow in the absence of biotin is due to the activation of a pyruvate carboxylase-independent pathway of oxaloacetate biosynthesis. It was also proposed that PEPCK, which normally functions as a gluconeogenic enzyme, may act as an anaplerotic enzyme involved in the synthesis of oxaloacetate. ROP was shown to be a key regulator of methanol metabolism when P. pastoris cells are cultured in YPM medium containing yeast extract, peptone and methanol but not YNBM medium containing yeast nitrogen base and methanol. In P. pastoris cells cultured in YPM, ROP functions as a transcriptional repressor of genes encoding key enzymes of the methanol metabolism such as the alcohol oxidase I. (AOXI). Deletion of the gene encoding ROP results in enhanced expression of AOXI and growth promotion while overexpression of ROP results in repression of AOXI and retardation of growth of P. pastoris cultured in YPM medium. Subcellular localization studies indicate that ROP translocates from cytosol to nucleus in cells cultured in YPM but not YNBM. To understand the mechanism of action of ROP, we examined its DNA-binding specificity. The DNA-binding domain of ROP shares 57% amino acid identity with that of Mxr1p, a master regulator of genes of methanol metabolism. We demonstrate that the DNA-binding specificity of ROP is similar to that of Mxr1p and both proteins compete with each other for binding to AOXI promoter sequences. Thus, transcriptional interference due to competition between Mxr1p and ROP for binding to the same promoter sequences is likely to be the mechanism by which ROP represses AOXI expression in vivo. Mxr1p and ROP are examples of transcription factors which exhibit the same DNA-binding specificity but regulate gene expression in an antagonistic fashion.

A fuel cell is an electrochemical power source with advantages of both the combustion engine and the battery. Like a combustion engine, a fuel cell will run as long as it is provided fuel; and like a battery, fuel cells convert chemical energy directly to electrical energy. As an electrochemical power source, fuel cells are not subjected to the Carnot limitations of combustion (heat) engines. Fuel cells bear similarity to batteries, with which they share the electrochemical nature of the power generation process and to the engines that, unlike batteries, will work continuously consuming a fuel of some sort. A fuel cell operates quietly and efficiently and, when hydrogen is used as a fuel, it generates only power and water. Thus, a fuel cell is a so called ‘zero-emission engine’. In the past, several fuel cell concepts have been tested in the laboratory but the systems that are being potentially considered for commercial developments are: (i) Alkaline Fuel Cells (AFCs), (ii) Phosphoric Acid Fuel Cells (PAFCs), (iii) Polymer Electrolyte Fuel Cells (PEFCs), (iv) Solid Polymer Electrolyte Direct Methanol Fuel Cells (SPE-DMFCs), (v) Molten Carbonate Fuel Cells (MCFCs) and (vi) Solid Oxide Fuel Cells (SOFCs). Among the aforesaid systems, PEFCs that employ hydrogen as fuel are considered attractive power systems for quick start-up and ambient temperature operations. Ironically, however, hydrogen as fuel is not available freely in the nature. Accordingly, it has to be generated from a readily available hydrogen carrying fuel such as natural gas, which needs to be reformed. But, such a process leads to generation of hydrogen contaminated with carbon monoxide, which even at minuscule level is detrimental to the fuel cell performance. Pure hydrogen can be generated through water electrolysis but hydrogen thus generated needs to be stored as compressed/liquefied gas, which is cost-intensive. Therefore, certain hydrogen carrying organic fuels such as methanol, ethanol, propanol, ethylene glycol and diethyl ether have been considered for fueling PEFCs directly. Among these, methanol with hydrogen content of about 12.8 wt.% (specific energy = 6.1kWh kg-1) is the most attractive organic liquid. PEFCs using methanol directly as fuel are referred to as SPE-DMFCs. But SPE-DMFCs suffer from methanol crossover across the polymer electrolyte membrane, which affects the cathode performance and hence the fuel cell during its operation. SPE-DMFCs also have inherent limitations of low open-circuit-potential and low electrochemical-activity. An obvious solution to the aforesaid problems is to explore other promising hydrogen carrying fuels such as sodium borohydride (specific energy = 12kWh kg-1), which has a capacity value of 5.67Ah g-1 and a hydrogen content of about 11wt.%. Such fuel cells are called direct borohydride fuel cells (DBFCs). This thesis is directed to studies on SPE-DMFCs and DBFCs

5 SUMMARY Context: Acute methanol poisoning is a life-threatening condition. Methanol is metabolized in the organism to formaldehyde and than to formic acid, which inhibits cytochrome c oxidase in mitochondria and thus contributes to the development of oxidative stress. Aim: To study the role of oxidative stress in the pathogenesis of acute neuronal damage to the central nervous system (CNS), in the development of long-term sequelae of methanol poisoning and chronic neurodegenerative processes in the years following acute methanol exposure. Material and Methods: Methanol intoxication was confirmed analytically in 55 patients included in he d ; hei age a he ime f i ning a 46.7 3.6 ea (9 female and 46 male ). All a ien , together with 41 control subjects, were examined in a prospective longitudinal cohort study. At admission, during hospitalisation, and at regular intervals after discharge during the follow-up, the patients were sampled for serum concentrations of lipid oxidative damage markers 4-hydroxy-trans-2- hexenal (HHE), 4-hydroxynonenal (HNE), malondialdehyde (MDA), and 8-isoprostane, for nucleic acids oxidative damage markers 8-hydroxy-2 -deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8- OHG), 5- (hydroxymethyl) uracil (5-OHMU), for proteins oxidative damage markers ortho-tyrosine (o- Tyr),...