La pile à combustible H+-SOFC (Protonic Conducting Solid Oxide Fuel Cell) basée surl’utilisation d’un électrolyte conducteur protonique peut représenter une alternative intéressanteà la pile SOFC qui présente actuellement le meilleur rendement. Cependant, la surtension à lacathode reste élevée et ce travail est dédié à la compréhension du mécanisme de réductionl'oxygène à cette électrode.Différents matériaux conducteurs mixtes O2- / e- de structures dérivées de la perovskite ABO3,tels que les doubles perovskites LnBaM2O5+d (Ln = Pr, Nd et Gd et M = Co et Fe) ainsi que lesphases de Ruddlesden-Popper A2MO4+d (Ln = Pr et Sr et M = Ni), ont été étudiés. Leur niveaude conductivité électronique ainsi que leur non-stoechiométrie en oxygène ont d’abord étédéterminées. Puis, à l’aide de la détermination des coefficients de diffusion de l’oxygène par laméthode de relaxation de conductivité électrique, leur conductivité ionique O2- a été estimée.Une étude électrochimique et plus spécialement la détermination des étapes limitant la réactionde réduction de l’oxygène à la cathode de pile H+-SOFC a ensuite permis de démontrer le rôledu proton dans le mécanisme de réaction pour les matériaux présentant les meilleuresperformances électrochimiques.Enfin, dans le cadre d’un projet ANR HPAC 2009 « CONDOR », des mono-cellules de piles H+-SOFC ont été mises en forme et des densités de puissance proche de 180 mW/cm² à 0.6 V à600°C ont été obtenues. / The H+-SOFC (Protonic Conducting Solid Oxide Fuel Cell) based on a protonic conductingelectrolyte can represent an interesting alternative to the SOFC fuel cell. Nevertheless, the highcathodic overpotential remains a severe drawback and this thesis is dedicated to the study of theunderstanding of the oxygen reduction at the cathode.Several mixed O2- / e- conductors derived from perovskite ABO3 such as double perovskiteLnBaM2O5+d and Ruddlesden Popper phases A2MO4+d were studied. Their electronic conductivityas well as their oxygen non-stoichiometry were first determined. Then, their oxygen diffusioncoefficients were measured using the electrical conductivity relaxation method and their O2-conductivity estimated. Rate determining steps of the oxygen reduction reaction weredetermined from electrochemical measurements and it was shown that proton is involved in theoxygen reduction for materials showing the best electrochemical performances.Finally, single H+-SOFC cells were developed in the framework of the ANR HPAC 2009 project“CONDOR” and power densities of about 180 mW/cm² at 0.6 V at 600°C were obtained.

Li-O2 batteries have attracted world-wide research interest as an appealing candidate for future energy supplies because they possess the highest energy density of any battery technology. However, such system still face some challenges for the practical application. One of the key issues is exploring highly efficient cathode materials for Li-O2 batteries. Here, a rolled-up technology associated with other physical or chemical methods are applied to prepare architectural nanomembranes for the cathode materials in Li-O2 batteries. The strain-release technology has recently proven to be an efficient approach on the micro/nanoscale to fabricate composite nanomembranes with controlled thickness, versatile chemical composition and stacking sequence. This dissertation first focuses on the synthesis of trilayered Pd/MnOx/Pd nanomembranes. The incorporation of active Pd layers on both sides of the poor conductive MnOx layer commonly used in energy storage systems greatly enhances the conductivity and catalytic activity. Encouraged by this design, Pd nanoparticles functionalized MnOx-GeOy nanomembranes are also fabricated, which not only improve the conductivity but also facilitate the transport of Li+ and oxygen-containing species, thus greatly enhancing the performance of Li-O2 batteries. Similarly, Au and Pd arrays decorated MnOx nanomembranes act as bifunctional catalysts for both oxygen reduction reaction and oxygen evolution reaction in Li-O2 batteries. Moreover, by introducing hierarchical pores on the nanomembranes, the performance of Li-O2 batteries is further promoted by porous Pd/NiO nanomembranes. The macropores created by standard photolithography facilitate the rolling process and the nanopores in the nanomembranes induced by a novel template-free method supply fast channels for the reactants diffusion. In addition, a facile thermal treatment method is developed to fabricate Ag/NiO-Fe2O3/Ag hybrid nanomembranes as carbon-free cathode materials in Li-O2 batteries. A competing scheme between the intrinsic strain built in the oxide nanomembranes and an external driving force provided by the metal nanoparticles is introduced to tune the morphology of the 3D tubular architectures which greatly improve the performance by providing continuous tunnels for O2 and electrolyte diffusion and mitigating the side reactions produced by carbonaceous materials.

The rechargeable Li-O2 battery has attracted interest due to its high theoretical energy density (about 10 times better than today’s Li-ion batteries). In this PhD thesis the cycling instability of the Li-O2 battery has been studied. Degradation of the battery has been followed by studying the interface between the electrodes and electrolyte and determining the chemical composition and quantity of degradation products formed after varied cycling conditions. For this in-house and synchrotron based Photoelectron Spectroscopy (PES) were used as a powerful surface sensitive technique. Using these methods quantitative and qualitative information was obtained of both amorphous and crystalline compounds. To make the most realistic studies the carbon cathode pore structure was optimised by varying the binder to carbon ratio. This was shown to have an effect on improving the discharge capacity. For Li-O2 batteries electrolyte decomposition is a major challenge. The stability of different electrolyte solvents and salts were investigated. Aprotic carbonate and ether based solvents such as PC, EC/DEC, TEGDME, and PEGDME were found to decompose during electrochemical cycling of the cells. The carbonate based electrolytes decompose to form a 5-10 nm thick surface layer on the carbon cathode during discharge which was then removed during battery charging. The degradation products of the ether based electrolytes consisted mainly of ether and carbonate based surface species. It is also shown that Li2O2 as the final discharge product of the cell is chemically reactive and decomposes carbonate and ether based solvents. The stability of lithium electrolyte salts (such as LiPF6, LiBF4, LiB(CN)4, LiBOB, and LiClO4) was also studied. The PES results revealed that all salts are unstable during the cell cycling and in contact with Li2O2. Decomposition layers thinner than 5 nm were observed on Li2O2. Furthermore, it is shown that the stability of the interface on the lithium anode is a chief issue. When compared to Li batteries (where oxygen levels are below 10 ppm) working in the presence of excess oxygen leads to the decomposition of carbonate based electrolytes to a larger degree.

D-Arginine dehydrogenase (DADH) catalyzes the oxidation of D-arginine to imino arginine using FAD as the cofactor. The enzyme is part of a recently discovered two-enzyme complex from Pseudomonas aeruginosa involved in arginine utilization. Function of the enzyme within the organism is unknown. Work on this enzyme has been undertaken to understand the structure as well as its reaction mechanism so as to eventually assign a function to the enzyme within the physiological context. In the reductive half-reaction 2 e- and 1 H+ are transferred from the amino acid substrate to FAD cofactor. In the oxidative half-reaction the reducing equivalents from the FAD cofactor are passed to an electron acceptor that is yet to be discovered. The enzyme has been established to have no reactivity with O2. Choline oxidase (CHO) from Arthrobacter globiformis is a well characterized member of Glucose-Methanol-Choline Superfamily that reacts with molecular O2. It catalyzes the oxidation of choline to glycine betaine mediated by betaine aldehyde intermediate using FAD as the cofactor and O2 as the oxidant to regenerate oxidized FAD for further reaction. Glycine betaine, the product of the reaction is an important osmolyte that regulates nutrients for plants under stressful conditions. Therefore it is of commercial interest to genetically engineer crops that do not typically possess competent pathways for glycine betaine synthesis. In this dissertation molecular details concerning the reductive half-eaction of DADH and oxidative half-reaction of CHO have been studied using a combination of steady state kinetics, rapid kinetics, pH, multiple substrates, mutagenesis, substrate deuterium and solvent isotope effects, viscosity effects or computational approaches. In DADH, the oxidation of amino acid substrate by FAD has been shown to most likely proceed via hydride transfer mechanism in the reductive half-reaction with Glu87, Tyr53, Tyr249 and His48 emerging as key players in substrate binding, catalysis or for up keeping the integrity of the FAD cofactor. In CHO, the oxidative half-reaction proceeds without stabilization of any reaction intermediates with H atom from reduced FAD and H+ from solvent or solvent exchangeable site occurring in the same kinetic step.

Un SGBD temporel doit offrir les fonctionnalités permettant aux applications de dater les informations et de gérer l'histoire de leur évolution. Cette thèse présente le modèle d'historiques TEMPOS et le prototype qui a été réalisé au dessus du SGBD O2. TEMPOS s'appuie sur un modèle du temps, qui permet de manipuler des valeurs temporelles, simples et complexes, exprimées dans différentes unités. Le jeu d'unité est extensible, et les opérations définies sont indépendantes des unités. La multiplicité des formes externes des valeurs temporelles est également prise en compte. Le modèle d'historiques proposé dans TEMPOS intègre les fonctionnalités essentielles attendues pour gérer la dimension historique des informations d'une base de données. La définition de différents types d'historiques (discret, en escalier, interpolé) permet de donner la signification des valeurs saisies et d'interpoler les autres valeurs. Ainsi, en TEMPOS, un historique est vu comme une chronique (séquence de valeurs datées), un domaine temporel d'observation, et une fonction d'interpolation. Le modèle permet diverses structurations des historiques basées sur le regroupement d'instants. Les opérations d'interrogation des historiques sont issues de l'extension temporelle des opérateurs de l'algèbre relationnelle et également d'une adaptation d'opérateurs sur les séquences, qui permettent en particulier de raisonner sur la succession dans le temps. Les opérations classiques de mise à jour sont étendues pour prendre en compte la dimension temporelle. Toutes les opérations sur les historiques sont définies de manière à être indépendantes de la représentation et de l'unité d'observation temporelle des historiques. Le prototype comprend une hiérarchie de classes implantant les types et les opérations proposés dans TEMPOS, et un préprocesseur TempOQL permettant de manipuler des valeurs temporelles dans des requêtes OQL.

La pile à combustible H+-SOFC (Protonic Conducting Solid Oxide Fuel Cell) basée surl'utilisation d'un électrolyte conducteur protonique peut représenter une alternative intéressanteà la pile SOFC qui présente actuellement le meilleur rendement. Cependant, la surtension à lacathode reste élevée et ce travail est dédié à la compréhension du mécanisme de réductionl'oxygène à cette électrode.Différents matériaux conducteurs mixtes O2- / e- de structures dérivées de la perovskite ABO3,tels que les doubles perovskites LnBaM2O5+d (Ln = Pr, Nd et Gd et M = Co et Fe) ainsi que lesphases de Ruddlesden-Popper A2MO4+d (Ln = Pr et Sr et M = Ni), ont été étudiés. Leur niveaude conductivité électronique ainsi que leur non-stoechiométrie en oxygène ont d'abord étédéterminées. Puis, à l'aide de la détermination des coefficients de diffusion de l'oxygène par laméthode de relaxation de conductivité électrique, leur conductivité ionique O2- a été estimée.Une étude électrochimique et plus spécialement la détermination des étapes limitant la réactionde réduction de l'oxygène à la cathode de pile H+-SOFC a ensuite permis de démontrer le rôledu proton dans le mécanisme de réaction pour les matériaux présentant les meilleuresperformances électrochimiques.Enfin, dans le cadre d'un projet ANR HPAC 2009 " CONDOR ", des mono-cellules de piles H+-SOFC ont été mises en forme et des densités de puissance proche de 180 mW/cm² à 0.6 V à600°C ont été obtenues.

Dans cette thèse, une approche microcinétique expérimentale est utilisée pour caractériser des étapes élémentaires impliquées dans l'oxydation de CO par O2 sur des catalyseurs à base de Pd et d'Au supportés sur oxydes métalliques et identifier celles qui contrôlent la vitesse de réaction. Sur un catalyseur 1,4%Pd/Al2O3, l'évolution de la production de CO2 (RCO2(t)) par oxydation des espèces CO adsorbées (2 linéaires L et 2 pontées P) a été suivie lors de cycles successifs formation - oxydation des espèces. Une période d'induction est observée, donnant un pic de CO2 caractérisé partm et RCO2m. L'étude de l'impact de différents paramètres expérimentaux sur tm et RCO2m: le tempsde désorption avant oxydation, la pression partielle de O2, la température et le prétraitement ducatalyseur a permis de caractériser les étapes superficielles impliquées. Un modèle cinétique basé surl'oxydation des espèces CO P par une espèce oxygène faiblement adsorbée formée sur des sites libéréspar la désorption et/ou l'oxydation des espèces CO L a permis d'interpréter ces impacts. Ce modèle aégalement permis d'interpréter les différences d'activités du catalyseur vis-à-vis de la réaction CO/O2en fonction de son prétraitement après réduction sous H2 à 713 K : un refroidissement sous hydrogènepermet d'obtenir des conversions de CO proches de 100% à 300 K en excès de O2 alors qu'unedésorption préalable à 713 K donne de faibles conversions (< 4%). Ces différences sont attribuées àune reconstruction de la surface des particules de Pd par désorption de l'hydrogène à 713 K.Sur Au supporté sur Al2O3 et SiO2, l'étude a porté sur la première étape de l'oxydation du CO:l'adsorption du CO. Sous certaines conditions (température et pressions) l'adsorption de CO à 300 Kentraîne une reconstruction progressive des particules d'or modifiant significativement les propriétésdes espèces adsorbées. La cinétique de cette reconstruction à 300 K est étudiée et interprétée

It has previously been stated that K+-ions in a plant cell have a counter-balancing role in which the efflux of K+-ions from the thylakoid lumen charge-balance the light-induced proton pumping that is known to occur across the thylakoid membrane, and this in turn stabilizes photosynthetic activity. In the present study, two different types of plants of the same ecotype (Col-0) of Arabidopsis thaliana have been studied: a wild-type and a T-DNA exon-mutant (tpk5-e) that has lost the expression of the protein known as Tandem-pore K+- channel (AtTPK5). The plants were grown in a hydroponic system under normal light conditions with 70% humidity. Homozygous (HM) tpk5-e mutant plants were screened using PCR and gene specific primers. Further, the photosynthetic activity was measured in 4 hour light-adapted plants and the photosynthetic activity of the tpk5-e mutant proved not to be significantly different in comparison to the wild-type when measuring the electron transport rate (ETR). Furthermore, the O2-evolution was also measured in 4 hour light-adapted plants and the tpk5-e mutant's O2-evolution proved to be significantly lower in the tpk5-e mutant in comparison to the wild-type under high light conditions. The plant fitness of the wild-type and tpk5-e mutant was also different judging from phenotypic traits such as chlorophyll expression. However, the measured chlorophyll amount of pigments chlorophyll a and b proved not to be significantly different in the tpk5-e mutant in comparison to the wild-type.

This study utilized Cu-catalysts to catalyze a NO reduction reaction using CH4 as a reductant. Due to CH4 being a weak reductant and is easily affected by O2 concentration, we undertook a series experiments with O2 concentration and promoters, so that we could better understand their influence. The experiment conditions were as follows : reaction temperature between 150¢J- 800¢J¡Fa catalysts weight of 0.5 g¡F total gas flow rate of 1000 ml/min¡Frelative humidity at 0.9 %¡Fan O2 concentration between 0 - 6%¡Fand CH4 concentration between 1000 - 10000 ppm. First, we sorted out the best metal carriers and calcining temperature, from this we decide to use £^-Al2O3 as a carrier with a calcining temperature under 500¢Jto produce our catalysts. During the O2 concentration experiment, when the inflow O2 concentration was below 1% (including 0% O2), Cu-catalysts reduce NO above 550¢J.The conversion reached a rate of 95 % at a temperature of 750¢J¡Fwhen the oxygen concentration was between 3% and 6% O2, catalysts reacted within 300 - 500¢J with NO converting to NO2¡Fat a concentration between 1.5% and 2% O2, NOx underwent reduction at 750¢J,and NOx conversion raised from 0 % to above 90%. Therefore in analyzing the experiment results, it shows that NOx will reduce violently when the O2 concentration is below 0.7% and while using CH4 as a reductant. This result was also apparent in O2 concentrations between 1.5 % and 2%. In the experiments of M/O ratio (the ratio of CH4 and O2 inflow), we found M/O ratio was not a deciding factor within the reaction mechanics, furthermore the limiting factor of O2 concentration decreases under 0.7%¡Fin addition it was also found that adding large amounts of CH4 could quicken the reduction process. Lastly, a mass balance was performed, which had a result over 70 %. In the experiments where Y¡BLa¡BSr¡BCo were added as promoters to the Cu-catalysts, we found that Cu-La/£^-Al2O3¡BCu-Sr/£^-Al2O3 and Cu-Co/£^-Al2O3 can accelerate O2 depletion. Henceforth, it is possible to deduce promoters will be a useful method in solving O2 limiting. In the comparison of metals loading methods, we found no difference in activity using separate-impregnation and co-impregnation methods, whereas in the BET and SEM co-impregnation experiments, there was a larger surface-area and dispersion.

Submitted by Ana Borges (ana.azevedo@udesc.br) on 2017-06-09T11:56:55Z No. of bitstreams: 1 Cristiane Mezaroba.pdf: 9118688 bytes, checksum: 7706a8529180fd844f20da89e3df3d57 (MD5) / Made available in DSpace on 2017-06-09T11:56:55Z (GMT). No. of bitstreams: 1 Cristiane Mezaroba.pdf: 9118688 bytes, checksum: 7706a8529180fd844f20da89e3df3d57 (MD5) Previous issue date: 2017-02-23 / CAPES / Plasma sterilization present effective and extensive microbial lethality, fast action, compatibility with various materials, high diffusion through porous substances and are non-polluting systems. The objective of this study was to evaluate if the inductive RF plasma and N2-O2 mixture is efficient for use in sterilization of polymer medical-hospital and dental materials, represented in this study by the polymer HDPE. It was also the objective of this study to evaluate the possible superficial modifications of HDPE after sterilization. HDPE films were used with spores of Geobacillus stearothermophilus, with ≅5,73x107 UFC/film. In the microbiological tests were used 20W and 40W power, 0.5 Torr pressure and exposure times of 2,5,10,15 and 20 minutes. Low temperature was maintained (T<40°C), and the results demonstrated sterilization efficiency. The samples were characterized by contact angle measurements, atomic force microscopy (AFM), scanning electron microscopy field emission (FEG-SEM) and Fourier transform infrared spectroscopy in the "Attenuated Total Reflectance" (FTIR-ATR) mode. The active species formed in plasma were identified by a system of optical emission spectroscopy (OES). / A esterilização por plasma têm oferecido vantagens em relação a outros métodos à baixa temperatura utilizados, a começar por alta eficácia e abrangente letalidade microbiana, ação rápida, compatibilidade com vários materiais, alta difusibilidade e é um sistema não poluente. O objetivo deste trabalho foi avaliar se o plasma RF indutivo (ICP) e mistura de N2-O2 é eficiente para uso em esterilização de materiais poliméricos médico-hospitalares e odontológicos, representado neste estudo pelo polímero PEAD. Também foi objetivo deste trabalho avaliar as possíveis modificações superficiais do PEAD após a esterilização. Foram utilizados filmes de PEAD com esporos de Geobacillus stearothermophilus, com ≅5,73x107 UFC/filme. Nos testes microbiológicos foram utilizadas potências de 20W e 40W, pressão de 0,5 Torr e tempos de exposição de 2,5,10,15 e 20 minutos. Foi mantida baixa temperatura (T<40°C), e os resultados demonstraram eficiência de esterilização. Os filmes de PEAD após esterilização foram caracterizados por medidas do ângulo de contato, microscopia de força atômica (AFM), microscopia eletrônica de varredura por emissão de campo (FEG-MEV) e espectroscopia no infravermelho por transformada de Fourier no modo “Refletância Total Atenuada” (FTIR-ATR). As espécies ativas formadas no plasma foram identificadas por um sistema de espectroscopia óptica de emissão (OES).