Photokatalytische Systeme sind in der Lage, lichtinduziert kleine Moleküle zu aktivieren. Für diesen komplexen Katalysevorgang ist ein Zusammenspiel mehrerer Komponenten wichtig, wie dem Photosensibilisator (PS) und dem Katalysator. Im Rahmen der vorliegenden Dissertation wurde auf verschiedenen Wegen versucht, photokatalytische Systeme auf Basis von Rhenium und 3d-Metallen zu optimieren. So konnten neue Komplexe auf Rheniumbasis synthetisiert und charakterisiert werden, welche zugleich als Photosensibilisator sowie Katalysator fungieren. Die Komplexe zeigen dabei nicht nur eine höhere Absorption, sondern auch eine höhere katalytische Produktivität, als deren mononuklearer Verwandte. Mittels DFT-Rechnungen und spektroskopischen Untersuchungen konnte gezeigt werden, dass ein kooperativer Vorgang stattfindet, bei dem eine Rheniumeinheit als PS, und eine als Katalysator agiert. Durch Zugabe eines externen PS konnte die katalytische Produktivität nochmals deutlich erhöht werden. Durch den zusätzlichen PS wird intermediär eine Rhenium-Rhenium-Spezies ausgebildet, welche CO2 kooperativ über beide Rheniumeinheiten aktivieren kann. Neben literaturbekannten PS auf Iridiumbasis wurden zudem neuartige Kupferphotosensibilisatoren genutzt. Verschiedene Derivate des Kupferphotosensibilisators wurden in der CO2-Reduktion und H2-Produktion getestet. Es zeigte sich, dass verschiedene elektronische Eigenschaften der PS Auswirkungen auf die Katalyseproduktivität haben. Zusätzlich wurden Katalysatoren auf Basis von 3d-Metallen konzipiert, welche abhängig von einem zusätzlichen PS sind. Bestrahlungsexperimente mit Iridium- und Kupfer-PS wurden durchgeführt und somit die Produktivität der einzelnen Katalysatoren bestimmt. Es konnte gezeigt werden, dass sowohl die Wahl des Liganden, als auch des Katalysatormetalls Einfluss auf Menge und Selektivität der Produkte hat. / Photocatalytic systems are capable of light-induced activation of small molecules. Among other things, this allows CO2 to be reduced to higher-energetic molecules. The interaction of several components, such as the photosensitizer (PS) and the catalyst, is important for this complex catalysis process. In this dissertation, attempts were made to optimize systems based on rhenium and 3d metals in various ways. One approach was to synthesize and characterize new rhenium-based complexes, which can act as PSs and catalysts at the same time. The complexes showed not only higher absorption but also higher catalytic activity than their mononuclear relative. Using DFT calculations and spectroscopic investigations, it was shown that a cooperative process takes place, in which one rhenium unit acts as a PS and one as a catalyst. By adding an external PS, the activity was significantly increased again. This forms a rhenium-rhenium species which is able to activate CO2 cooperatively via both rhenium units. In addition to iridium-based PS known from the literature, novel copper photosensitizers were also used for this purpose. In order to get a better understanding of the interaction of both components, different derivatives of the copper photosensitizer were tested in the activity towards CO2 reduction and H2 evolution reaction. The electronic influence of the PS on the catalytic activity could be elucidated by means of Stern-Vollmer quenching studies and DFT calculations. In addition, catalysts based on 3d metals were designed. Iron, cobalt and nickel were used as the central atom together with two different macrocyclic ligands. These monomolecular compounds are dependent on a PS. Furthermore, irradiation experiments with iridium and copper PS were carried out and the activity of the individual catalysts was thereby determined. It was shown that the choice of the ligand as well as the catalyst has an influence on the quantity and selectivity of the resulting products.

Non-thermal plasmas are considered to be very promising for the initiation of chemical reactions and a vast amount of experimental work has been dedicated to plasma assisted hydrocarbon conversion processes, which are reviewed in the fourth chapter of the thesis. However, current knowledge and experimental data available in the literature on plasma assisted liquid hydrocarbon cracking and gaseous hydrocarbon decomposition is very limited. The experimental methodology is introduced in the chapter that follows the literature review. It includes the scope and objectives section reflecting the information presented in the literature review and the rationale of this work. This is followed by a thorough description of the design and construction of the experimental plasma reformer and the precise experimental procedures, the set-up of hydrocarbon characterization equipment and the development of analytical methods. The methodology of uncertainty analysis is also described. In this work we performed experiments in attempt the cracking of liquid hexadecane into smaller liquid hydrocarbons, which was not successful. The conditions tested and the problems encountered are described in detail. In this project we performed a parametric study for methane and propane decomposition under a corona discharge for COx free hydrogen generation. For methane and propane a series of experiments were performed for a positive corona discharge at a fixed inter-electrode distance (15 mm) to study the effects of discharge power (range of 14 - 20 W and 19 – 35 W respectively) and residence time (60 - 240 s and 60 – 303 s respectively). A second series of experiments studied the effect of inter-electrode distance on hydrogen production, with distances of 15, 20, 25, 30 and 35 mm tested. The analysis of the results shows that both discharge power and residence time, have a positive influence on gaseous hydrocarbon conversion, hydrogen selectivity and energy conversion efficiency for methane and propane decomposition. Longer discharge gaps favour hydrogen production for methane and propane decomposition. A final series of experiments on corona polarity showed that a positive discharge was preferable for methane decomposition.

Empirical algorithms are developed using high-quality GO-SHIP hydrographic measurements of commonly measured parameters (temperature, salinity, pressure, nitrate, and oxygen) that estimate pH in the Pacific sector of the Southern Ocean. The coefficients of determination, R-2, are 0.98 for pH from nitrate (pH(N)) and 0.97 for pH from oxygen (pH(Ox)) with RMS errors of 0.010 and 0.008, respectively. These algorithms are applied to Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) biogeochemical profiling floats, which include novel sensors (pH, nitrate, oxygen, fluorescence, and backscatter). These algorithms are used to estimate pH on floats with no pH sensors and to validate and adjust pH sensor data from floats with pH sensors. The adjusted float data provide, for the first time, seasonal cycles in surface pH on weekly resolution that range from 0.05 to 0.08 on weekly resolution for the Pacific sector of the Southern Ocean.

New phosphonium and ammonium ionic liquids were prepared for use in two green applications. Ionic liquids are generating considerable current interest as media for electrochemical processes such as electrodeposition, which can be used to create thin films of a variety of compounds. For the first time, silicon deposition has been achieved in the phosphonium ionic liquid triethyl(2-methoxyethyl)phosphonium bis(trifluoromethylsulfonyl)amide (P201-TFSI). Subsequently, silicon has been deposited from a wide variety of precursors in order to optimize the thickness and morphology of the deposited films. The silicon films electrodeposited in the phosphonium ionic liquid show marked differences from those deposited in organic solvents, imidizolium and pyrrolidinium based ionic liquids. Phosphonium and ammonium ionic liquids were also investigated for use in carbon dioxide capture. Task-specific ionic liquids have shown great promise as agents for the physisorption and chemisorption of CO2 from combustion gas streams. Efforts to synthesize new task specific ionic liquids with multiple amine functionalities for CO2 capture are reported. Four different reaction pathways were explored for the synthesis of these materials. While this goal was not achieved in this work, task-specific phosphonium and ammonium ionic liquids offer the promise of opening up new areas in ionic liquid research. / text

The purpose of this research is to develop a dataset for some of the most important fire characteristics, namely CO2 yield, CO yield, HCN yield, soot yield and heat of combustion for probabilistic analysis and modelling. Raw data in time series are required to mechanically reduce experimental data into yields (kg/kg) and effective heats of combustion (MJ/kg), which are expressions for the amount of products generated per unit mass of fuel. Mass loss rate thresholds were applied to all tests to define the beginning and end of tests. These species yields and heat of combustions were then grouped by material compositions and fitted with distribution functions to produce distributions curves. As fire species productions and heat of combustions are dependent on the fire conditions as it develops, different yields are expected at different fire stages. These have been identified as the growth (G), transition (T), and smouldering (S) stages in this research. These values are also compared against, and are generally in agreement with, other research data. Nonetheless, some discrepancies have occurred and require further information to ascertain the material characteristics and combustion conditions. In conclusion, design recommendations for these fire characteristics have been made for several material groupings and verified against other research results. Certain physical and chemical limitations exist for combustions and have not been reflected in the fitted distribution, including stoichiometric yields and unlimited air yields. As such, species yields and heat of combustions beyond these values should not be considered in fire engineering design and analysis. Research results on HCN including all required data parameters for yield conversions were difficult to obtain and require further research efforts. Tube furnace results were initially investigated. Unfortunately, without a continuous mass record, has proved to be challenging in producing reliable mass loss rate profiles for yield conversions. A semi-automated data reduction application UCFIRE was also used. However, certain technical difficulties were encountered and require modifications to broaden its applicability.

No description available.

This study examined the effects of elevated CO2 and its interaction with drought and nitrogen fertilizer on the growth, production and nodulation of the leguminous crop lentil (Lens culinaris Medic) cultivars ILL7979 and ILL6994 (Idlib 3). Plants were grown under ambient and elevated CO2 at full and limited irrigation conditions in both open top chambers, which were later proven to be unreliable because of CO2 leakage, and tightly sealed and ventilated chambers which were reliable. Destructive harvests at anthesis and at maturity were conducted and results from sealed chambers at maturity showed that above ground dry weight was increased by an average of 12% under elevated CO2, but this increase was not statistically significant.

A necessidade atual do mercado brasileiro para aumentar a oferta de gás incentiva a comunidade científica nacional no desafio de desenvolvimento de novas rotas tecnológicas, visando aumentar o aproveitamento do gás natural. Tal desafio é acompanhado por uma demanda mundial dos países signatários do Protocolo de Quioto (ratificado em 2005) para a redução das emissões de gases de efeito estufa. Apesar de o Brasil não apresentar nenhuma meta de redução, no primeiro período deste Protocolo (2008 a 2012), o setor do petróleo (atividade de E&P), através de suas companhias operadoras, que atuam no país, já estabeleceram metas corporativas para emissão evitada de gases de efeito estufa, em suas instalações de produção (maior predominância das unidades marítimas de produção). O presente trabalho aborda a análise técnica e econômica de um processo proposto de separação e captura de dióxido de carbono (CO2), através de estudo de caso (Primeira e Segunda Proposição) de simulação de processo, em uma instalação marítima de produção de petróleo, comparativamente a sua ausência (Caso Base). A Primeira Proposição considera a separação e a captura do CO2 oriundo tanto do gás natural produzido, quanto do gás de queima de uma turbina a gás. A Segunda Proposição considera a separação e a captura do CO2 oriundo somente do gás natural produzido. Até o momento, no Brasil, ainda não foram desenvolvidas tecnologias adequadas para a captura do CO2, em instalações marítimas de produção de petróleo. Adicionalmente a regulação atual (Portaria nº104/2002 da ANP) limita o potencial de utilização do CO2 que existe na composição do gás natural comercializado no país, pelo fato de não diferenciar em sua especificação técnica, os usos deste importante combustível. Os resultados obtidos nesta tese, com a utilização de simulador de processo de uso comercial mostraram emissões evitadas de CO2 para atmosfera de 55 % (caso Segunda Proposição que apresentou maior viabilidade econômica), em relação ao resultado obtido para o Caso Base. Este relevante resultado equivale a uma emissão evitada de aproximadamente 241 x 103 t/ano, para uma única unidade piloto proposta. De acordo com o estudo de análise econômica apresentado, a Segunda Proposição (VPL US$ 15,3 x 106) foi melhor do que a da Primeira Proposição (VPL: US$ 13,9 x 106) ambos usando o Caso Base como referência. Dentre os ganhos esperados com o uso desta nova tecnologia destacam-se: redução do consumo interno e das perdas de gás natural, emissão evitada de CO2 e hidrocarbonetos para a atmosfera, além do aumento das práticas de armazenamento de gás e CO2, em reservatórios geológicos depletados de petróleo. Estima-se que num cenário futuro, com a implantação deste novo processo proposto, em instalações marítimas de produção de petróleo, uma relevante contribuição de emissões evitadas de gases de efeito estufa possa ocorrer na área de E&P de petróleo no Brasil. / The current Brazilian market needs to increase the natural gas supply to incentive the national scientific community to the challenge of developing new technologies routes aiming increase the utilization of the produced natural gas. Such challenge is followed by a world demand from signatory countries of the Kyoto Agreement (ratified in 2005) to reduce the greenhouse gas emissions. In spite of, the Brazil does not have any reduction goal, in the first period (2008 to 2012) the oil sector (E&P activity), by their oil operators companies that works in our country, has already established corporative goals to avoided greenhouse gas emissions in their production facilities (bigger predominance of offshore production unities). The present work approaches the economic and technical evaluation of a carbon dioxide (CO2) separation and capture proposal process (First and Second Proposal Case) comparatively your absence (Base Case). The First Case consider the CO2 separation and capture both the produced gas and exhausted gases of one turbine driven by gas. The Second Case consider only the CO2 separation and capture from the produced gas. At the present, in Brazil, it has not been developed yet suitable technologies, for such use, and the CO2 is normally disposal to the atmosphere. Moreover, the present Regulation (104/2002 ANP Decree) limit the potential of CO2 use existing in the gas composition that is marketed in the country, due to not differentiate the uses of this important fuel. The results obtained of this thesis, by using a process simulator of commercially use showed CO2 avoided emissions of 55 % to the atmosphere (Second Proposal Case that shows the best economic evaluation) related to the result obtained from the Base Case. This relevant result is equivalent in mass flow, to the avoidance emission of roughly 241 x 103 tons per year, for a single pilot unity proposal. According the economic evaluation study, the Second Proposal Case (VPL:US$ 15,3 x 106) was better than the First Case (VPL: US$ 13,9 x 106), using the Case Base as reference. Within the benefits expected with the use of this new technology are the following: reduction both the internal gas consumption and natural gas losses (atmospheric disposal), emissions avoided of CO2 and hydrocarbons, beyond the increase of CO2 and gas storage practices in offshore depleted oil fields. It is estimated, in future scenery, with the implantation of this new proposal process in offshore production unities, relevant contribution of avoided greenhouse gases emissions can occur in oil E&P tasks in Brazil.

No description available.

With the emission of carbon dioxide (CO2) becoming an international worry due its role in climate change, solutions such as CO2 capture and storage technologies are needed to decrease the emissions. The main proportion of CO2 gas emissions is from fossil fuel combustion in a range of industries, including power generation. To develop the CO2 capture system for these operations, new materials are needed for CO2 capture. Metal-organic framework (MOF) materials have porous crystal structures containing organic molecules (organic ligands) linked to each other by metalcontaining nodes. The large internal surface area can be exploited for the adsorption of small gas molecules, and for this reason MOFs may be ideal candidate materials for CO2 capture and gas separations. Thousands of MOF materials have been reported, with different combinations of the ligands and metals and with the capability of forming many different network topologies. Experimentally it is very difficult to study the gas absorption dynamics, interaction and gas adsorption capacity for the large number of materials. This problem can be solved by simulations. The aim of the thesis is to develop a systematic simulation method to screen the MOF properties and CO2 adsorption capacity and interaction dynamics at different environment. The molecular dynamics (MD) method with parameterised force fields was used to study the interactions between CO2 molecules and one class of the MOFs, zeolitic imidizolate frameworks (ZIFs) with zinc as the metal cation. To develop the model, the atom charges have been developed by using the distributed multipole analysis (DMA) method based on ab initio DFT calculations for molecules and clusters. The intermolecular forces were developed by fitting against the MP2 calculations of small clusters of the metal cations and molecular ligands. In order to evaluate the models I simulated the gas-liquid coexistence curve of CO2 and showed that it is consistent with experiments. I also simulated the pure ZIF structures on changing both temperature and pressure, demonstrating the stabilities of the structures but also showing the existence of displacive phase transitions. I have used this approach to successfully study CO2 absorption in a number of ZIFs (from ZIF-zni, ZIF-2, ZIF-4, ZIF-8 and ZIF-10) using MD. The gas absorption capacity and dynamics have been investigated under 25 bar and 30 bar, 200 , showing a promising uptake of CO2. The results have shown that CO2 capacity is mainly determined by the pore sizes and pore surfaces, in which a higher capacity is associated with a higher pore surface. The intermolecular distance of CO2 inside the pores and channels have been investigated in the saturation state. It has been shown that the distance is approximately 4 Å. The attraction force is from the interaction between CO2 and the imidazolate ligands. In addition, the systematic studies of the saturated ZIF system gave the minimum diameters for CO2 adsorption which is approximately 4.4 Å. This interaction has caused the gate opening effects, with the imidazolate ligands being pushed to be parallel to the CO2 molecules and opening up to allow more gas molecules go through the channels that connect the pore structures. This gate opening effect also explains the phase transition in ZIF-10 caused by CO2 molecules in our simulation, and can be applied to predict phase transitions in other materials with similar structure such as ZIF-7 and ZIF-8. The dynamics have also shown that the gas diffusion velocity is determined by the pore structure as well and by the accumulated layers of CO2 on the surface prior to being pushed in toward the centre of the material layer by layer. The de-absorption processes have also been studied in these materials by decreasing the pressure from 25 bar to 1 bar under at same temperature. The results indicate that the de-absorption is a reverse process of absorption. The structure of ZIF-10 went through a phase transition induced by CO2 recovered after the guest molecules had been released. The de-absorption can be accelerated by increasing the temperature.