Ce travail vise à étudier la transestérification de l'huile de tournesol pour la production de biodiesel et le vaporeformage du glycérol pour la production d'hydrogène renouvelable. Les oxydes mixtes Mg-Al prépares par voie hydrotalcite ont été choisis comme supports catalytiques. Pour la production de biodiesel, les effets du traitement thermique et de la méthode de préparation pour l'incorporation de calcium ont été étudiés. Le catalyseur Ca600/Mg₄Al₂HT calciné à 600°C, préparé par imprégnation de 40 wt% de Ca sur le support Mg₄Al₂ non calciné, a montré les meilleures performances catalytiques en raison de ses propriétés basiques améliorées. Pour le vaporeformage catalytique du glycérol, l'activité des oxydes de métaux purs imprégnés par le Ni a d'abord été étudiée, puisque les oxydes de métaux purs sont souvent utilisés comme supports catalytiques. Le catalyseur Ni/ZrO₂ s'est révélé le plus efficace pour la production d'hydrogène. Pour le vaporeformage du glycérol en présence d'oxydes mixtes obtenus par voie hydrotalcite, les catalyseurs au Ru-Mg-Al ont été étudiés. L'effet de la méthode de préparation (imprégnation ou greffage) sur l'activité catalytique a été étudié. Le catalyseur préparé par imprégnation permettait une plus grande accessibilité à la phase active. Pour des catalyseurs Ni-Mg-Al, les supports ont été modifiés par du lanthane. Le catalyseur Ni/Mg₆Al₁.₆La₀.₄ était le plus performant en raison de sa basicité accrue et de son interaction métal-support. Les activités des catalyseurs Ni/ZrO₂ et Ni/Mg₆Al₁.₆La₀.₄ ont été comparées. Les deux catalyseurs ont produit des rendements en hydrogène similaires. Moins de coke a été produit sur le catalyseur préparé par voie hydrotalcite, en raison de sa basicité supérieure. Un test de stabilité à 600°C a montré la désactivation du catalyseur Ni/Mg₆Al₁.₆La₀.₄ après 6 heures. Lors de l'optimisation des conditions de réaction sur le catalyseur Ni/Mg₆Al₁.₆La₀.₄, une amélioration significative de la stabilité a été observée, étendant ainsi sa durée de vie à 24 heures. / This work aims to study the transesterification of sunflower oil for biodesel production and the steam reforming of glycerol for renewable hydrogen production. Mg-Al hydrotalcite derived mixed oxides were chosen as catalytic support materials given their known basicity, thermal stability and low cost. Only one active phase was studied for biodiesel production (Ca) and two different active phases (Ru and Ni) for glycerol steam reforming. The various prepared catalysts were characterized by different techniques such as X-Ray Diffraction (XRD), specific surface area determination by BET method, Fourier Transform Infrared Spectroscopy (FTIR), H₂-Temperature Programmed Reduction (H₂-TPR), CO₂-Temperature Programmed Desorption (CO₂-TPD) and Simultaneous Thermogravimetric-Differential Scanning Calorimetry (TG-DSC). For biodiesel production, the effects of thermal treatment and the preparation method for Ca incorporation were both studied. The catalyst that showed the best catalytic performance was an uncalcined Mg₄Al₂ support impregnated with 40 wt% Ca followed by a calcination at 600°C (Ca/600Mg₄Al₂HT) due to its enhanced basic properties. After several optimization steps over this catalyst, the optimum conditions for biodiesel synthesis were: a methanol to oil molar ratio of 15:1, a catalyst to oil ratio of 2.5 wt% and a reaction time of 6 hours which gave a FAME yield of 95%. The properties of the produced biodiesel were studied and found to be in good agreement with ASTM (American Society for Testing and Materials) requirements. For the catalytic steam reforming of glycerol, the activity of NI-based pure metal oxides (Ni/CeO₂, Ni/Y₂O₃, Ni/ZrO₂) was first studied as pure metal oxides are commonly used as support materials. The effect of the support was evaluated and the Ni/ZrO₂ catalyst was found to be the most efficient for hydrogen production. To study the effect of the zirconia phase, a tetragonal Ni/ZrO₂ was also prepared. The tetragonal catalyst was less active for hydrogen production compared to the monoclinic catalyst. A stability test at 600°C also showed the desactivation of the tetragonal Ni/ZrO₂ after 6 hours on stream. For the catalytic steam reforming of glycerol using Mg-Al hydrotalcite derived mixed oxides, Ru-based Mg-Al catalysts were first studied. The effect of the preparation method (impregnation vs grafting) on the catalytic activity of Ru-Mg-Al catalysts was studied. The catalyst prepared by the impregnation method resulted in a better catalytic activity than the catalyst prepared by the grafting method as it allowed a higher accessibility of the active phase. For the Ni-based Mg-Al catalysts, the hydrotalcite supports were modified with La to study the effects of promoter addition on catalytic properties and activity. The bimetallic effect (1%Ru-5%Ni) and effect of a higher Ni loading (15 wt%) were also studied. The 5 wt% Ni impregnated on a La modified Mg-Al support (Ni/Mg₆Al₁.₆La₀.₄) catalyst was the most efficient for hydrogen production due to its enhanced basicity and metal-support interaction. The activities of the most efficient catalysts, Ni/ZrO₂ and Ni/Mg₆Al₁.₆La₀.₄, were compared. Both catalysts produced similar hydrogen yields. Differences in glycerol conversion to gaseous products were attributed to a higher formation of liquid by-products over the hydrotalcite support compared to the zirconia support. Nevertheless, less coke was produced over the hydrotalcite catalyst given its higher basicity. A stability test at 600°C showed the desactivation of the Ni/Mg₆Al₁.₆La₀.₄ catalyst after 6 hours on stream. Upon optimization of the reaction conditions on Ni/Mg₆Al₁.₆La₀.₄, a significant improvement in the stability was observed as the catalyst lasted for 24 hours on steam.Therefore, Ni/Mg₆Al₁.₆La₀.₄ could be a promising candidate for industrial application.

O dióxido de cério (CeO2), pode apresentar condutividade iônica e eletrônica (condutor misto) em temperaturas relativamente baixas (considerando a faixa de trabalho 1000°C de uma SOFC). Esta característica torna este material promissor para uso em células a combustível de óxido sólido (SOFC ou CCOS) assim como em catalisadores. Vale destacar que em altas temperaturas o dióxido de cério puro é um mau condutor iônico, contudo pode-se obter um aumento significativo com a substituição estrutural do íon cério (Ce+4) por outro íon metálico de menor valência (La+3 e Ca+2). O estudo proposto consiste em sintetizar óxido de cério dopado com lantânio e cálcio com características microestruturais e elétricas adequadas para uso em uma CCOS. Utilizando o método de síntese de combustão foi estudado a influência que o excesso de combustível (sacarose) pode proporcionar nas características finais dos pós cerâmicos. A caracterização dos pós foi realizada pelas técnicas de raios-X (DRX), área superficial especifica (BET), análise termogravimétrica (TGA), Microscopia Eletrônica de: Varredura (MEV) e Transmissão (MET), Microscopia de Calefação (MC) e por fim a análise elétrica por meio da Espectroscopia de Impedância Eletroquímica (EIE). Os principais resultados mostraram que a técnica de síntese por combustão é um método eficiente para obtenção de pós nanoparticulados, bem dispersos e com elevada homogeneidade. Observou-se ainda que a troca do tipo de dopante assim como o teor de combustível utilizado na síntese interfere diretamente nas propriedades microestruturais, físicas e elétricas dos compostos finais a base de céria dopada. As amostras apresentaram comportamento condutor em baixas temperaturas (500°C) o que viabiliza sua utilização como catalizadores e também em CCOS após tratamentos térmicos em atmosferas adequadas para aplicação como eletrodos ou eletrólitos. Os resultados também demonstram que a céria dopada com cálcio tem características que se torna viável a substituição do lantânio para uso em uma CCOS. / The cerium dioxide (CeO2) has ionic and electronic conductivity (mixed conductor) properties at relatively low temperatures (considering a working range of 1000°C for a SOFC). These characteristics make this material appropriate for use as anode in solid oxide fuel cells (SOFC or CCOS). It should be mentioned that pure cerium dioxide is a bad ionic conductor in high temperatures, but we have a significant increase with the structural substitution of the cerium ion (Ce+4) by another metal ion of lower valence (in its crystalline lattice). The proposed study consisted in the synthesis of ceria oxide with lanthanum and/ or calcium with microstructural and electrical characteristics, suitable for use in a CCOS. Using the combustion synthesis, the influence of excess of fuel (sucrose) on the final characteristics of the ceramic powder has been analyzed. The characterization of the powders was realized using X-ray (XRD), specific surface area (BET), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Electron Microscope Transmission (TEM), Microscope Heating (HSM) and Electrochemical Impedance Spectroscopy (EIS). The main results showed that the combustion synthesis technique is an efficient method to obtain nanoparticulate and well dispersed powders with high homogeneity. It was observed that the exchange of the dopant type as well as the fuel content used in the synthesis interferes directly in the microstructural, physical and electrical properties of the final compounds of ceria doped. Therefore, the calcium doped ceria has interesting characteristics for use in a CCOS.

Orientador: Alexandre Zirpoli Simões / Resumo: Devido à problemática das intoxicações com monóxido de carbono ser responsável pelo maior tipo de envenenamento do século 21, objetivou-se a produção de materiais nanoestruturados a base de céria, pura e dopada com lantânio (La 3+ ), através do método hidrotermal assistido por micro-ondas com posterior deposição na forma de filmes, para caracterização como dispositivos sensores na detecção de atmosfera de CO, por meio da técnica de sonda de duas pontas. O método de síntese empregado foi eficaz na produção de nanopartículas, com dimensões inferiores a 10 nm, apresentando elevada cristalinidade, caracterizada por um ordenamento periódico a curta e longas distâncias, além da ausência de fases secundárias, comprovadas pelas caracterizações realizadas por difratometria de raios-X (DRX), bem como pelas técnicas de espectroscopias Raman, Infravermelho, Ultravioleta- Visível ou ainda por Ressonância Paramagnética de Elétrons. Os filmes depositados apresentaram uma resposta frente ao gás CO extremamente rápida e seletiva, com tempos de resposta em 54, 12, 5.5 e 2 s para as amostras pura e dopadas com lantânio em 4, 8 e 12%, respectivamente. Além da resposta elétrica, os filmes apresentaram ainda uma resposta óptica, com destaque para a amostra com 8%, a qual muda de cor em menos de 1s, a 380 °C sob pressão de 5 mmHg de CO, tornando-se promissores sensores de gás com resposta dupla (óptica e elétrica). / Doutor

CO, volatile organic compounds, and polyaromatics areubiquitous air pollutants that give rise to deleterious healthand environmental effects. Such compounds are emitted, forinstance, by the combustion of wood, particularly fromsmall-scale heating appliances. Total catalytic oxidation isconsidered to be an effective approach in controlling theseemissions, however, some problems remain such as thenon-availability of catalysts with low-cost, high activity andstability in prevailing conditions. Hence, this thesis aims atthe development of oxidation catalysts and improvedunderstanding of their behaviour. The catalytic activity was evaluated for the oxidation of amixture of CO, naphthalene (or ethylene), and methane inpresence of carbon dioxide, water, oxygen and nitrogen. Variouscharacterisation techniques, including Temperature-ProgrammedReduction and Oxidation, BET-Surface Area Analysis, X-RayDiffraction, X-Ray Photoelectron Spectroscopy, RamanSpectroscopy and Scanning and Transmission Electron Microscopywere used. In the first part of this thesis, catalysts based on metaloxides (MnOx, CuO) and/or a low amount of noble metals (Pt, Pd)supported on alumina washcoat were selected. It was shown thatPt and Pd possessed a superior catalytic activity to that ofCuO and MnOxfor the oxidation of CO, C10H8and C2H4, while for the oxidation of CH4, CuO was largely more active than noble metals,and MnOxas active as Pd and Pt. Some mixed metaloxide-noble metal catalysts showed decreased activity comparedto that of noble metals, however, a higher noble metal loadingor a successive impregnation with noble metals led to positivesynergetic effects for oxidation. Deactivation of the catalysts by thermal damage and sulphurpoisoning is addressed in the second part of the dissertation.An alumina washcoat was found to be well anchored to themetallic support after thermal treatment at 900°C due tothe growth of alumina whiskers. The sintering of the washcoatwas accelerated after high temperature treatments in thepresence of metal catalysts. In addition, alumina was found toreact with CuO, particularly in presence of noble metals at900°C, to form inactive CuAl2O4. However, MnOxcatalyst benefits from the more active Mn3O4phase at high temperature, which makes it asuitable active catalyst for the difficult oxidation of CH4. Pt sintering was delayed when mixed with CuO,thus giving more thermally resistant catalyst. The mixed metaloxide-noble metal catalysts showed higher activity afterpre-sulphation of the catalysts with 1000 ppm SO2in air at 600°C or during activitymeasurement in presence of 20 ppm SO2in the gas mixture, compared to single componentcatalysts. In some cases, the activities of the mixed catalystswere promoted by pre-sulphation due to the presence of sulphatespecies. Thermal stabilisation of the catalytic componentsand thealumina by promotion of La in the washcoat is discussed in thethird section. The stabilising effect of La at high temperatureis also compared to that of Ce added in the catalysts for otherpurposes. Due to its better dispersion, La contributed to thethermal stabilisation of the alumina washcoat and its activecomponents to a higher extent than Ce did. La provided a betterdispersion and a higher saturation of metal oxides in thealumina support, and at the same time stabilised the activityof the catalysts by preventing undesirable solid-phasereactions between metal oxide and alumina. In addition, La wasfound to enhance the dispersion and the oxygen mobility of CeO2. Cu-Ce interactions were found to promotesubstantially the CO oxidation due to an increase of thestability and reducibility of Cu species. Synergetic effectswere also found between Ce and La in the washcoat of CuO-Ptcatalyst, which facilitated the formation of reduced Pt and CeO2, thus enhancing significantly the catalyticactivity compared to that of a Pt only catalyst. The last part was an attempt to demonstrate the potential ofa catalyst equipped with a pre-heating device in a full-scalewood-fired boiler for minimising the high emissions during thestart-up phase. During the first ten minutes of the burningcycle a significant reduction of CO and hydrocarbons wereachieved. <b>Keywords</b>: wood combustion, catalysts, total oxidation,manganese, copper, platinum, palladium, lanthanum, cerium, CO,VOC, methane, deactivation, thermal stability, sulphurdioxide.

The aim of this study was to produce zirconium diboride (ZrB2) and other metal borides such as lanthanum hexaboride (LaB6) and cerium hexaboride (CeB6) by magnesiothermic reduction (reaction of metal oxide, boron oxide and magnesium) using volume combustion synthesis (VCS) and mechanochemical process (MCP). Production of ZrB2 by VCS in air occurred with the formation of side products, Zr2ON2 and Mg3B2O6 in addition to MgO. Formation of Zr2ON2 was prevented by conducting VCS experiments under argon atmosphere. Wet ball milling was applied before leaching for easier removal of Mg3B2O6. Leaching in 5 M HCl for 2.5 hours was found to be sufficient for removal of MgO and Mg3B2O6. By MCP, 30 hours of ball milling was enough to produce ZrB2 where 10% of excess Mg and B2O3 were used. MgO was easily removed when MCP products were leached in 1 M HCl for 30 minutes. Complete reduction of ZrO2 could not be achieved in either production method because of the stability of ZrO2. Hence, after leaching VCS or MCP products, final product was composed of ZrB2 and ZrO2. Formation of LaB6 and CeB6 were very similar to each other via both methods. Mg3B2O6 appeared as a side product in the formation of both borides by VCS. After wet ball milling, products were leached in 1 M HCl for 15 hours and pure LaB6 or CeB6 was obtained. As in ZrB2 production, 30 hours of ball milling was sufficient to form these hexaborides by MCP. MgO was removed after leaching in 1 M HCl for 30 minutes and the desired hexaboride was obtained in pure form.

Lanthanum orthoborate (LaBO3) has aroused interest of scientists for many decades because of their remarkable properties and potential applications. They provide favorable magnetic properties for various applications. Additionally, they possess high VUV transparency and exceptional optical damage when they compose with rare earth elements. This study comprises the synthesis of pure lanthanum orthoborate, europium, dysprosium and terbium doped lanthanum orthoborate by two methods with v three fuels, citric acid, glycine and urea. LaBO3 has already been synthesized by various methods, however / in this work, two alternative roads are suggested, microwave assisted method and sol-gel microwave assisted method. The second task of the work is to find out the best luminescent product by altering the synthesis conditions, type of the doping material and the doping amount of the rare earth element. For the microwave assisted combustion method, urea was used as a fuel. After synthesis in the microwave oven, further heating up to 950&deg / C was performed. For the microwave assisted sol-gel method, citric acid and glycine were used. After obtaining the gel mixture, the product is synthesized in the microwave oven at 1200 W for ten minutes. For this route, again 950&deg / C heating for 2 hours was performed. Powder X-ray diffraction method was employed for the characterization of the material. The morphological properties of doped and un-doped materials were studied by SEM (Scanning Electron Microscope) and TEM (Transmission Electron Microscope). Besides, FT-IR (Fourier Transform Infra red) spectrometry analyses were performed to detect the differences in the bond structure and also to identify the corresponding bands. Luminescence studies were performed to detect the best emission intensities by using Fluorescence spectroscopy. The XRD patterns confirmed that lanthanum orthoborate production was successful by three precursors. The space group is Pnma, and the crystal system is orthorhombic with the unit cell dimensions / a= 5.8761(1)

<p>CO, volatile organic compounds, and polyaromatics areubiquitous air pollutants that give rise to deleterious healthand environmental effects. Such compounds are emitted, forinstance, by the combustion of wood, particularly fromsmall-scale heating appliances. Total catalytic oxidation isconsidered to be an effective approach in controlling theseemissions, however, some problems remain such as thenon-availability of catalysts with low-cost, high activity andstability in prevailing conditions. Hence, this thesis aims atthe development of oxidation catalysts and improvedunderstanding of their behaviour.</p><p>The catalytic activity was evaluated for the oxidation of amixture of CO, naphthalene (or ethylene), and methane inpresence of carbon dioxide, water, oxygen and nitrogen. Variouscharacterisation techniques, including Temperature-ProgrammedReduction and Oxidation, BET-Surface Area Analysis, X-RayDiffraction, X-Ray Photoelectron Spectroscopy, RamanSpectroscopy and Scanning and Transmission Electron Microscopywere used.</p><p>In the first part of this thesis, catalysts based on metaloxides (MnO_x, CuO) and/or a low amount of noble metals (Pt, Pd)supported on alumina washcoat were selected. It was shown thatPt and Pd possessed a superior catalytic activity to that ofCuO and MnO_xfor the oxidation of CO, C₁₀H₈and C₂H₄, while for the oxidation of CH₄, CuO was largely more active than noble metals,and MnO_xas active as Pd and Pt. Some mixed metaloxide-noble metal catalysts showed decreased activity comparedto that of noble metals, however, a higher noble metal loadingor a successive impregnation with noble metals led to positivesynergetic effects for oxidation.</p><p>Deactivation of the catalysts by thermal damage and sulphurpoisoning is addressed in the second part of the dissertation.An alumina washcoat was found to be well anchored to themetallic support after thermal treatment at 900°C due tothe growth of alumina whiskers. The sintering of the washcoatwas accelerated after high temperature treatments in thepresence of metal catalysts. In addition, alumina was found toreact with CuO, particularly in presence of noble metals at900°C, to form inactive CuAl₂O₄. However, MnO_xcatalyst benefits from the more active Mn₃O₄phase at high temperature, which makes it asuitable active catalyst for the difficult oxidation of CH₄. Pt sintering was delayed when mixed with CuO,thus giving more thermally resistant catalyst. The mixed metaloxide-noble metal catalysts showed higher activity afterpre-sulphation of the catalysts with 1000 ppm SO₂in air at 600°C or during activitymeasurement in presence of 20 ppm SO₂in the gas mixture, compared to single componentcatalysts. In some cases, the activities of the mixed catalystswere promoted by pre-sulphation due to the presence of sulphatespecies.</p><p>Thermal stabilisation of the catalytic componentsand thealumina by promotion of La in the washcoat is discussed in thethird section. The stabilising effect of La at high temperatureis also compared to that of Ce added in the catalysts for otherpurposes. Due to its better dispersion, La contributed to thethermal stabilisation of the alumina washcoat and its activecomponents to a higher extent than Ce did. La provided a betterdispersion and a higher saturation of metal oxides in thealumina support, and at the same time stabilised the activityof the catalysts by preventing undesirable solid-phasereactions between metal oxide and alumina. In addition, La wasfound to enhance the dispersion and the oxygen mobility of CeO₂. Cu-Ce interactions were found to promotesubstantially the CO oxidation due to an increase of thestability and reducibility of Cu species. Synergetic effectswere also found between Ce and La in the washcoat of CuO-Ptcatalyst, which facilitated the formation of reduced Pt and CeO₂, thus enhancing significantly the catalyticactivity compared to that of a Pt only catalyst.</p><p>The last part was an attempt to demonstrate the potential ofa catalyst equipped with a pre-heating device in a full-scalewood-fired boiler for minimising the high emissions during thestart-up phase. During the first ten minutes of the burningcycle a significant reduction of CO and hydrocarbons wereachieved.</p><p><b>Keywords</b>: wood combustion, catalysts, total oxidation,manganese, copper, platinum, palladium, lanthanum, cerium, CO,VOC, methane, deactivation, thermal stability, sulphurdioxide.</p>

A variety of benefits motivate the development of epitaxial metals, among which include the ability to design fully integrated layer structures where metallic films and nanostructures can be embedded into the cores of optoelectronic devices. Applications include high-performance tunnel-junctions, epitaxial transparent Ohmic contacts, photomixer material, and thermoelectrics. Additionally, the integration of metallic nanostructures and films into optoelectronic devices has shown potential for improving device performance and functionality through sub-wavelength confinement of plasmonic modes and enhancement of light/matter interactions. The rare-earth monopnictide (RE-V) material system can be integrated epitaxially with conventional zincblende III-V substrates under normal growth conditions, resulting in high-quality, thermodynamically stable interfaces. The RE-V semimetals span a range of optical, electrical, and structural properties, making them ideal for integration into III-V-based optoelectronic devices and applications. In this dissertation, high-quality epitaxial LuAs, LaAs and La(x)Lu(1-x)As films and nanostructures were grown and characterized for their structural, electrical, optical, and plasmonic properties. Through a sweep of alloy film compositions of the RE-V alloy material La(x)Lu(1-x)As, the ability to produce tunable epitaxial metals was demonstrated, with a range of peak transmission spectra from near- to mid-infrared wavelengths, plasmonic response in the mid-infrared, moderate resistivity, and lattice-matching potential to many relevant III-V substrates. Additionally, there is a great deal of interest in developing techniques to produce optoelectronic devices that are not restricted by substrate lattice constant. Many epitaxial approaches have been tried, with moderate success; however, growing low defect-density heteroepitaxial materials with differing crystal structures and highly-mismatched lattice parameters is extremely challenging, and such structures suffer from poor thermal properties and reliability issues. A general approach is needed for thin metamorphic buffer layers with minimal threading dislocations that simultaneously have low thermal resistance for effective heat-sinking and device reliability. An investigation was conducted into the use of RE-V nanostructure superlattices towards the reduction of dislocation density in highly-mismatched III-V systems. / text

Low cost silicates with apatite-structure (general formula of apatite A10-xM6O26±δ, where A = rare earth or alkaline earth and M= Si, Ge, P, V..) have been proposed recently as promising solid electrolyte materials (oxygen ion conductors) for use at intermediate temperature solid oxide fuel cells (SOFCs). These materials exhibit sufficiently high ionic conductivity (e.g. ~ 0.01 S cm-1 at 700 oC), which is dominated by the interstitial site mechanism and can exceed that of yttria-stabilized-zirconia (YSZ), the solid electrolyte used in state-of-the-art SOFCs. The apatite structure is tolerant to extensive aliovalent doping, which has been applied for improving ionic conductivity. In this work are presented results concerning synthesis, conductivity and catalytic characterization of Fe- and/or Al-doped apatite type lanthanum silicates (ATLS) of the general formula La10-zSi6-x-yAlxFeyO26±δ as well as electrochemical characterization of interfaces of ATLS pellets with perovskite and Ni-based electrodes. The aim was to investigate the properties of these ATLS material, in particular as it concerns their potential use as SOFC components or as catalysts in oxidation reactions. The conductivity of pellets prepared from ATLS powders synthesized via four different methods and having different grain size was measured under air and at different temperatures in the range 600 -850 oC, aiming to identification of the effect of composition (doping), method of synthesis, grain size and pellet sintering conditions. For electrolytes of the same composition, those prepared via mechanochemical activation exhibited the highest conductivity, which was improved with increasing Al- and decreasing Fe-content. In state-of-the-art SOFCs perovskite electrodes are used as cathodes and Ni-based electrodes as anodes, thus electrochemical characterization of perovskite and Ni-based/ATLS interfaces was carried out. As it concerns perovskite/ATLS interfaces, the characterization focused on the study of the open circuit AC impedance characteristics of a La0.8Sr0.2Ni0.4Fe0.6O3-δ/La9.83Si5Al0.75Fe0.25O26±δ interface, at temperatures 600 to 800 oC and oxygen partial pressures ranging from 0.1 to 20 kPa. Under the aforementioned conditions, it was observed that the impedance characteristics of the interface were determined by at least two different processes, corresponding to two partially overlapping depressed arcs in the Nyquist plots. The polarization conductance of the interface was found to increase with increasing temperature as well as with increasing oxygen partial pressure, following a power law dependence. The electrochemical characterization of Ni-based electrodes/ATLS interfaces involved study of the electrochemical characteristics of NiO-apatite cermet electrodes as well as a Ni sputtered electrode interfaced with Al- or Fe-doped apatite electrolytes, under hydrogen atmospheres. The impedance characteristics of these electrodes were found to be determined by up to three different processes, their relative contribution depending on the electrode microstructure, Ni content (as it concerns the cermet electrodes), temperature, hydrogen partial pressure and applied overpotential. Aiming to investigation of potential catalytic properties of ATLS materials the catalytic activity for CO combustion of a series of ATLS powders was studied. For this purpose, two series of apatite-type lanthanum silicates La10-xSi6-y-zAlyFezO27-3x/2-(y+z)/2 (ATLS), undoped or doped with Al and/or Fe, were synthesized via sol-gel and modified dry sol-gel methods and tested as catalysts for CO combustion. The experiments revealed that the ATLS powders were catalytically active for CO combustion above approximately 300 oC, with light-off temperatures T50 (50% conversion of CO) ranging from 505 to 629 oC. The study focused on the effect on catalytic activity of the synthesis method and doping with Al and/or Fe. Non-doped ATLS with stoichiometric structure, namely La10Si6O27 prepared via the sol-gel method, exhibited the highest catalytic activity for CO oxidation among all tested compositions, the comparison being based on the measured catalytic rate (expressed per surface area of the catalyst) under practically differential conditions. Compared to La-Sr-Mn-O and La-Sr-Co-Fe-O perovskite powders, the tested ATLS powders exhibited lower catalytic activity for CO oxidation. / -

Ce travail de thèse est focalisé sur la détermination, de manière non-destructive, d'interfaces profondément enterrées dans des empilements multi-couches utilisés dans les conditions de technologie réelles au travers d'une méthode innovante basée sur la photoémission avec utilisation de rayons-x de haute énergie (HAXPES) et l'analyse du fond continu inélastique. Au cours de cette thèse, une procédure numérique a été développée pour quantifier la correspondance entre la mesure du fond continu faite par HAXPES et la simulation du fond continu représentative d'une distribution en profondeur donnée. Cette méthode permet de trouver la distribution en profondeur d'un élément grâce à une procédure semi automatisée. Dans un premier temps cette méthode a été testée en étudiant une couche ultra fine de lanthane enterrée à une profondeur >50 nm dans un dispositif de grille métallique high-k. L'influence des paramètres utilisés lors de l'analyse y est étudiée et révèle l'importance principale d'un paramètre en particulier, la section efficace de diffusion inélastique. La combinaison de mesures HAXPES avec l'analyse du fond continu inélastique utilisant cette nouvelle méthode permet d'augmenter la profondeur de sonde jusqu'à un niveau sans précédent. Ainsi l'échantillon peut être sondé jusqu'à 65 nm sous la surface avec une haute sensibilité à une couche nanométrique. Dans un second temps, la méthode précédemment validée d'analyse de fond continu inélastique est combinée avec une étude haute résolution des niveaux de cœur dans un échantillon servant de source dans un transistor à haute mobilité. Les deux analyses sont complémentaires puisqu'elles permettent d'obtenir la distribution en profondeur des éléments ainsi que leur environnement chimique. Le résultat donne une description complète des diffusions élémentaires dans l'échantillon suivant les différentes conditions de recuit. / This thesis tackles the challenge of probing in a non-destructive way deeply buried interfaces in multilayer stacks used in technologically-relevant devices with an innovative photoemission method based on Hard X-ray PhotoElectron Spectroscopy (HAXPES) and inelastic background analysis. In this thesis, a numerical procedure has been implemented to quantify the matching between a HAXPES measured inelastic background and a simulated inelastic background that is representative of a given depth distribution of the chemical elements. The method allows retrieving depth distributions at large depths via a semi-automated procedure. First, this method has been tested by studying an ultra-thin layer of lanthanum buried at depth >50 nm in a high-k metal gate sample. The influence of the parameters involved in the analysis is studied unraveling the primary importance of the inelastic scattering cross section. The combination of HAXPES with inelastic background analysis using this novel method maximizes the probing depth to an unprecedented level, allowing to probe the sample up to 65 nm below the surface with a high sensitivity to a nm-thick layer. Second, the previously-checked inelastic background analysis is combined with that of high resolution core-level spectra in the case of the source part of a high electron mobility transistor. The two analyses are complementary as they allow retrieving the elemental depth distribution and the chemical state, respectively. The result gives a complete picture of the elemental intermixing within the sample when it is annealed at various temperatures. / Denne afhandling omhandler problemet med at probe dybt begravede grænseflader i multilags stacks, som bruges i teknologisk relevante devices, med en innovativ fotoemissions metode, der er baseret på Hard X-ray PhotoElectron Spectroscopy (HAXPES) og analyse af den uelastiske baggrund. I afhandlingen er en numerisk procedure blevet implementeret til at kvantificere forskellen mellem en HAXPES målt uelastisk baggrund og en modelleret baggrund, som svarer til en given dybdefordeling af atomerne. Metoden muliggør, med en halv-automatisk procedure, at bestemme dybdefordelingen i store dybder. Metoden er først blevet testet ved at studere et ultra-tyndt lag af lanthan, som er begravet i en dybde > 50 nm i en high-k-metal-gate prøve. Indflydelsen af parametrene der ingår i analysen er blevet studeret for at opklare den primære betydning af det anvendte uelastiske spredningstværsnit. Kombinationen af HAXPES med analyse af den uelastiske baggrund og brug af den nye numeriske metode giver en hidtil uset probe-dybde, som giver mulighed for at probe den atomare sammens ætning i op til 65 nm dybde under overfladen og med høj følsomhed af et kun nm tykt lag. Dernæst er den uelastiske baggrundsanalyse blevet kombineret med højopløst core-level spektroskopi for at studere de aktive dele i en høj-elektronmobilitets transistor. De to analyser er komplementære, idet de henholdsvis bestemmer den atomare fordeling og atomernes kemiske bindingstilstand. Resultatet giver et fuldstændigt billede af atomernes omfordeling i prøven når denne opvarmes til forskellige temperaturer.