Depuis la découverte de la première exoplanète en 1995 par Mayor et Queloz, le nombre de planètes extrasolaires découvertes n'a cessé d'augmenter, pour dépasser les 1000 planètes à la fin de l'année 2013. Depuis le début des années 2000, la détection s'est accompagnée d'une volonté de caractérisation de l'atmosphère des exoplanètes. Les méthodes utilisées jusqu'ici sont la spectroscopie de transit primaire et l'étude des émissions thermiques en transit secondaire ou via l'étude des courbes de phase. L'objet de cette thèse s'inscrit dans cette recherche de caractérisation des atmosphères exoplanétaires, en s'intéressant à une méthode jusqu'ici inexplorée : l'analyse des émissions thermosphériques, i.e. les émissions de la haute atmosphère induites par les entrées énergétiques, flux extrême UV de l'étoile hôte et précipitations électroniques principalement. La première partie de cette thèse s'intéresse aux émissions thermosphériques de la Terre primitive avec une approche basée sur la modélisation. Le but étant la détermination des différentes émissions de la Terre à travers son histoire, afin de disposer de proxies pour la recherche et la caractérisation d'exoplanètes telluriques. Dans un premier temps nous avons calculé l'émission de l'atmosphère primordiale de la Terre irradiée par le Soleil jeune dans la raie Lyman Alpha. Nous avons montré que la raie planétaire, principalement formée par diffusion cohérente, montre un rapport d'émission avec le Soleil de l'ordre de 10-8, inaccessible aux observations, avec les instruments actuels ou de prochaine génération. Ce premier résultat nous à conduit à étudier la faisabilité d'une méthode indirecte de détection d'une couronne dense d'hydrogène autour d'une planète tellurique possédant une atmosphère de CO2 par les émissions des sous-produits de dissociation et d'ionisation de CO2. Les calculs menés sur la raie verte de l'oxygène (état O1S) et le doublet UV de CO2+ (état B2Σu+) ont montré que ces émissions présentaient des contrastes de l'ordre de 10^-12 avec le Soleil dans le cas d'une Terre primitive, et de l'ordre de 10^-6-10^-8 pour une planète tellurique proche d'une naine M. La conclusion générale des ces investigations est que les raies fines (atomiques ou moléculaires) des émissions thermosphériques sont trop faibles pour être détectées par les instruments actuels. Une voie possible serait l'étude des bandes d'émission moléculaires, qui nécessite une meilleure compréhension de la distribution en intensité des différentes bandes à travers le spectre, compréhension qui passe par l'étude expérimentale de ces émissions. C'est dans ce cadre que se situe la deuxième partie de cette thèse, qui s'intéresse à l'analyse spectroscopique de la Planeterrella, simulateur d'aurores boréales initialement développé à des fins pédagogiques. Nous avons réalisé une étude spectroscopique à basse et haute résolution de l'air, afin de caractériser les émissions présentes dans l'expérience d'une part, et aussi de disposer d'un spectre de référence qui servira à terme de test pour un code Monte Carlo développé pour étudier le dispositif expérimental, la caractérisation du dispositif constituant une étape nécessaire pour faire de la Planeterrella un objet d'étude scientifique. Enfin, la spectroscopie basse résolution du CO2 a été réalisée, avec des applications potentielles à Mars. / Since the discovery of the first exoplanet in 1995 by Mayor and Queloz, the number of extrasolar planets discovered has continuously grown up, to overtake 1000 planets at the end of 2013. Since the beginning of the 2000's, came with the detection the will to characterize the atmospheres of these exoplanets. Until now, the methods used are the primary transit spectroscopy and the study of the thermal emissions in secondary transit or using phase curves. The purpose of this thesis belongs to that search for characterizing exoplanetary atmospheres, by looking at a method unexplored until now: the study of the thermospheric emissions, i.e. emissions from the upper atmosphere induced by the energetic entries, mainly the extreme UV flux and the electronic precipitations. The first part of this thesis concerns the thermospheric emissions of the primitive Earth with an approach based on modeling. The goal is the determination of the several emissions of the Earth through its history in order to have proxies for the search and the characterization of telluric exoplanets. Initially we calculated the emission of the primary atmosphere of the early Earth under the young Sun in the Lyman Alpha line. We showed that the planetary line in mainly due to coherent diffusion and that the emission ratio between the planet and the Sun in this line is of about 10-8, far from the capabilities of current or next generation instruments. This first result lead us to study the feasibility of an indirect method to infer the presence of dense hydrogen corona surrounding a telluric planet with a CO2-dominated atmosphere, by studying its influence on the emissions of two CO2 by-products. The calculations carried out on the oxygen green line (O1S state) and the UV doublet of CO2+ (B2Σu+ state) showed that theses emissions present contrasts of about 10^-12 with the young Sun in the case of a primitive Earth, and of about 10^-6-10^-8 for a close-in telluric planet around a M dwarf. The general conclusion of the investigations is that the thermospheric emissions of thin (atomic or molecular) lines are too weak to be detected. A possible way could be the study of the molecular bands, of which emissions need to be better understood, especially concerning the intensity distribution of the several bands through the spectrum. This comprehension implies experimental studies of these emissions. The second part of this thesis lies in this scope and concerns the spectroscopic analysis of the Planeterrella, an aurora borealis simulator initially designed for outreach purpose. We made a spectroscopic study at low and high resolution with air, in order to characterize the emissions existing in the experiment, and also to have a reference spectrum which will be a final test for a Monte Carlo code developed to study the experimental device, the characterization of this device being a necessary step for the Planeterrella to become suitable for scientific purpose. Finally, we made a low resolution spectroscopic study of carbon dioxide, with potential applications to Mars.

Philosophiae Doctor - PhD / Fossil fuels are part of fuels that are formed from natural processes and they are called non-renewable sources of energy. These include natural gas, coal and oil. They have been used for decades to produce energy globally. However, there are some factors that related with the use of fossil fuels which results in an increase in the requirement of large amounts of energy. In addition, the use of fossil fuels as energy source has a negative impact on the environment and they cannot be reused. It is expected that at some point they will run out. Thus, a need for a renewable, clean and plentiful source of energy is urgent. Solar energy is one of the energy sources that may overcome fossil fuel drawbacks.

Hydrogen is a vital component in several different chemical reactions as well as a potential fuel source for the future. The water gas shift (WGS) reaction converts CO and water to hydrogen and CO2. The objective of this work is to first, characterize the potential benefits of the addition of lanthanum oxide (lanthana) to the iron-chromium-copper (Fe-Cr-Cu) oxide catalysts industrially used in high temperature water gas shift processes, and second, analyze these catalysts using in-situ UV-Visible spectroscopy. The benefits of each component in the catalyst are discussed as well as potential benefits from the addition of lanthana. Lanthana is a rare earth oxide that dramatically increases the surface area of the iron based WGS catalysts, and small concentrations of other rare earth oxides (i.e. cerium) have been shown to increase the rate of desorption of CO2 from iron surfaces (Hu Yanping 2002). Lanthana has similar chemical properties to other rare earth oxides tested and has not been previously tested as an additive to the WGS catalyst. Therefore catalysts with 0, 1, 2, 5, 10, and 20 wt% lanthana were made via a co-precipitation method in order to measure changes in activity, physical stability, and thermal stability. Catalyst characterization techniques utilized include electron dispersive X-ray spectroscopy (EDX), temperature programmed reduction (TPR) with hydrogen, and nitrogen physisorption (BET). The kinetic analysis was performed utilizing both mass spectroscopy (MS) and gas chromatography (GC). The addition of 1 wt% lanthana to the Fe-Cr-Cu catalysts increases WGS reaction rates of the catalyst at 425°C and 350°C, however the 0% La catalyst has the highest rates at 375°C and 400°C. The 0% La catalyst shows significant drop off in rate at 425°C, suggesting that the lanthana provides a small thermal stabilizing, i.e. the addition of lanthana prevents catalyst sintering at higher temperatures. Traditionally, chromia acts as the sole thermal stabilizer in these catalysts. The addition of large amounts of lanthana inhibits the chromia stabilizing effect, however small additions of lanthana appear to have an additional catalyst promotional effect without interfering with the chromia thermal stabilization. The increased WGS reaction rates at higher temperatures could allow for greater throughput of reactants in industrial settings. Higher concentrations of lanthana decrease the activity due to what is believed to be disruption of the chromia stabilizing effect as well as reduced amount of the active phase of catalyst. In-situ UV-Visible analysis shows that the oxidation state of the iron in the catalyst has a direct correlation to the UV-Visible light absorbance of the surface of the iron catalyst. Extent of reduction is traditionally measured with a synchrotron which is significantly more expensive than UV-Vis spectroscopy. This study uses the more economical UV-Vis spectrometer to determine similar information. The lanthana doped catalysts show an over-reduction of iron during WGS conditions (i.e. rapid reduction of Fe2O3 to Fe3O4 and FeO).

The structural and functional roles of lanthana in unsupported iron-based catalysts for the high-temperature water-gas shift reaction and Fischer-Tropsch synthesis were investigated. The performance of the catalysts with varying lanthana contents was based on their activity, selectivity, and stability. With regard to the former reaction, extent of reduction of the iron in Fe2O3/Cr2O3/CuO/La2O3 water-gas shift catalysts is a key parameter that was characterized using UV-visible spectroscopy. Minor addition of lanthana (<0.5 wt%) produces more active and stable catalysts apparently because it stabilizes the iron-chromium spinel, increases the surface area of the reduced catalysts, enhances the reduction of hematite to the magnetite active phase, and facilitates the adsorption of CO on the surface of the catalyst modeled by an adsorptive Langmuir-Hinshelwood mechanism. Statistical 95% confidence contour plots of the adsorption equilibrium constants show that water adsorbs more strongly than CO, which inhibits the reaction rate. A calibration curve that correlates the oxidation state of surface iron domains to normalized absorbance of visible light was successfully generated and applied to the water-gas shift catalysts. UV-visible studies indicated higher extent of reduction for surface Fe domains for the catalysts promoted with 1 wt% of lanthana and showed potential to be a more convenient technique for surface chemistry studies than X-ray absorption near edge spectroscopy (XANES). Lanthana addition to iron-based Fischer-Tropsch catalysts enhances the olefin-to-paraffin ratio, but decreases their activity, stability, and selectivity to liquid hydrocarbons. Adding lanthana at the expense of potassium reduces the water-gas shift selectivity and enhances the activity and stability of the catalysts. Finally, a model that simulates heat and mass transfer limitations on the particle scale for the Fischer-Tropsch reaction applicable at lab-scale suggests optimal operating and design conditions of 256°C, 30 bar, and 80 mirons are recommended for higher selectivity to liquid hydrocarbons. The model considers pressure drop, deactivation, pore diffusion, film heat transfer, and internal heat transfer when solving for the optimal conditions, and maps them as functions of design variables. This model can be up-scaled to provide guidance for optimal design of commercial-size reactors.

No description available.

Owing to the importance of gold nanoparticles in catalysis, designing of them has become a major focus of the researchers. Most of the current methods available for the synthesis of gold nanoaprticles (GNPs) suffer from the challenges of polydispersity, stability and use of toxic and harmful chemicals. To overcome these limitations of conventional methods, in our present study, we made an attempt to design a method for the green synthesis of monodispersed and stable gold nanoparticles by sugars which act as reducing and stabilizing agent. Characterization of synthesized nanoparticles was done by using various analytical techniques such as transmission electron microscope (TEM), dynamic light scattering spectroscopy (DLS), UV-Vis spectroscopy, scanning electron microscopy and electron dispersion spectroscopy. The synthesized sugar GNPs (S-GNPs) were spherical in shape and in the size range of 10 ± 5 nm. p-Nitrophenol reduction assay was used as a model system to determine the catalytic reduction activity of various sugar capped GNPs, monosaccharides (fructose), disaccharide (sucrose) and trisaccharide (raffinose) GNPs. The effect of temperature and the size of ligand on catalytic activity was also evaluated at different temperature using UV-Vis spectrometer. Using the spectroscopic data, rate constant (k) for three sugar capped GNPs was determined followed by its activation energy (Ea) and exponential (A) factor.

Magister Scientiae - MSc (Chemistry) / The increasing cost of fossil fuel energy production and its implication in environmental pollution and climate change created high demand for alternative and renewable sources of energy. This has led to great interest in research in the field of photovoltaic or solar cells Due to the abundance of sunlight, the technology is sustainable, non-polluting and can be implemented at places where power demand is needed, for example in rural areas. Solar cell devices that have been commercialized are currently based on silicon technology, involving the use of monocrystalline, polycrystalline and amorphous silicon. Although they produce highly efficient solar cells, the cost of Si solar cells is too high. Second generation solar cell materials such as cadmium telluride and third generation materials such as perovskites and organic polymers have been receiving much attention recently. However, they lack the efficiency of Si solar cells. This research proposes the development of high energy conservation photovoltaic cells from novel low-cost organosilicon polymers. The aim was to develop novel highly branched organosilane polymers such as poly(3-hexythiophene), polydi(thien-2-yl)dimethylsilane, poly(3-hexyl- [2,2'] bithiophenyl-5-yl)-dimethyl-thiophen-2yl-silane) as electron donors along with zinc oxide nanorod as the electron acceptor which were able to bring the efficiency of the resultant photovoltaic cell close to that of current Si solar cell. / 2021-08-31

Dyes for inkjet printing are typically of the chromonic type. Chromonic mesophases have gained considerable attention as a well-defined group of lyotropic mesogens with different properties from conventional amphiphiles. While extensive research has been dedicated to the field of surfactant liquid crystals, structural and aggregation studies of chromonics have only emerged as a topic of interest within the last few years. The liquid crystalline structures in aqueous solutions of commercial Cu - phthalocyanine and black dyes have been examined using a combination of optical microscopy, UV-vis spectroscopy, nuclear magnetic resonance, wide- and small-angle X-ray diffraction and electronic paramagnetic resonance with a view to examining the phase behaviour of the chromonic mesophases formed over a broad range of concentrations and temperatures. These studies were performed in order to resolve outstanding problems concerning structural properties of these systems. Optical microscopy allowed us to identify the liquid crystalline phases and to construct the phase diagram. The observations show that both of these dyes form nematic mesophase above 15% wt / wt% dye. The small-angle diffraction data confirmed that the nematic phase for the black dye is maintained throughout the 16-25% composition range. A further increase in concentration leads to the formation of the hexagonal phase. The Cu – phthalocyanine dye also formed a nematic phase at low concentrations, with the aggregates undergoing a phase transition to an orientationally ordered chromonic liquid crystal phase at high dye concentration. These studies showed that this ordered phase possessed hexagonal symmetry. The wide-angle X-ray results demonstrated that aggregation involved π-π stacking of the molecules into columns. An additional reflection at ca. 6.8Å was observed for the black dye, which is believed to arise from “head – to – tail” packing of the molecules within the aggregates (a similar phenomenon observed in other azo dyes, e.g. Edicol Sunset Yellow).The densities of both dyes were measured over the studied range of concentrations. This enabled us to calculate the parameters of the aggregates within the hexagonal mesophase. A comparison between the area of the molecule and the cross-section of the aggregates showed that the aggregates of both dyes were the unimolecular stacks.

No description available.

Este trabalho é dividido em duas partes. Na primeira parte são estudadas moléculas isoladas, na segunda, moléculas em meio solvente. Em sua primeira parte, métodos de mecânica quântica de alto nível de correlação são utilizados para caracterizar o estado fundamental da molécula de CaC. Propriedades elétricas e óticas desta molécula, como também da molécula de MgH, são obtidas usando-se o método de campo finito. O estudo dessas moléculas é de interesse para a Astrofísica. A segunda parte deste trabalho foca o estudo teórico do solvatocromismo da molécula de 4-[(4-dimethylamino)phenyl)imino]-2, 5-cyclohexadien-1-one, ou DIA (Dimethylaminoindoaniline). Esta molécula apresenta também uma grande variação da sua primeira hiperpolarizabilidade medida em solução. Sabe-se que ela existe em solução como uma combinação de duas formas extremas: a forma com separação de cargas eno e a forma neutra ceto. Após otimizarmos teoricamente as estruturas dessas duas formas, realizamos uma simulação Monte Carlo em um número de moléculas de solventes polares e apoiares. A análise da estrutura do solvente, em torno de cada soluto, é realizada usando-se funções de distribuição radial de pares. É feita, também, a análise das pontes de hidrogênio para cada estrutura eno ou ceto. Estruturas supermoleculares, envolvendo o soluto com as moléculas mais próximas e, em separado. com as moléculas ligadas por pontes de hidrogênio, são usadas como entrada para cálculos semi-empíricos de mecânica quântica da primeira transição eletrônica de absorção e da primeira hiperpolarizabilidade. Apenas superestruturas estatisticamente descorrelacionadas foram usadas no cálculo. Os resultados são analisados e comparados com resultados experimentais em solução e com resultados teóricos em fase gasosa. Todas as interpretações sugerem que a estrutura eno é responsável pelos espectros experimentais de absorção UV-visível, tanto em solvente polares quanto em apoiares. A estrutura eno tem também uma primeira hiperpolarizabilidade calculada que concorda adequadamente com aquelas observadas em alguns solventes. Para clorofórmio a primeira hiperpolarizabilidade do DIA é dez vezes maior que em outros solventes. / This work is divided in two parts. In the first part isolated molecules are studied, in the second part the interest is in molecules in solvent media. In the first part of this work, high level quantum mechanical correlation methods are employed to characterise the ground state of the CaC molecule. Electrical and optical properlies of this molecule and also of the MgH molecule are obtained using the finite field method. The study of these molecules is of interest to Astrophysics. The second part of this work focuses on the theoretical study of the solvatochromism of the 4-[(4-dimelhylamino)phenyl)imino]-2, 5-cyclohexadien-1-one molecule, or DIA (Dimethylaminoindoaniline). This molecule also presents a large variation of its measured first hyperpolarizability in solution. It is known that in solution this molecule exists in a combination of two extreme forms, the chargeseparated eno form and the neutral kelo form. After these two structures are theoretically optimised, a Monte Carlo simulation is performed in a number of polar and non-polar solvent molecules. Analysis of1 the solvent structure around each solute is performed using radial distribution function. Hydrogen bonding analysis for each eno or keto structure is also carried out. Supermolecular structures involving the solute and the nearest solvent molecules and, separately, the hydrogen bonded molecules, are used as input to quantum mechanical semi-empirical calculations of the first electronic absorption transition and the first hyperpolarizability. Only statistically non-correlated superstructures were used in the calculation. The results are analysed and compared to experimental results in solution and theoretical results in gas-phase. All interpretations suggest that the eno structure is responsible for the experimental UV-Visible absorption spectrum, both in polar and non-polar solvents. The eno structure has also a calculated first hyperpolarizability that agrees well with that observed for some solvents. For chloroform the first hyperpolarizability of DIA is ten times greater than in other solvents.