In this thesis, the morphology and electric potential of pristine and gold covered surfaces with the fluorite structure are investigated by non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM). The pristine (111) surface of calcium difluride is prepared by cleaving. Cleavege ledges are composed of short alternating type I and type II steps having different atomic structures and polarities. With respect to the stoichiometric terrace, the surface potential is slightly reduced at ledges predominately composed of type I steps, while the potential of ledges predominantly composed of type II steps is significantly higher. Pristine (111) surfaces of ceria single crystals and ceria thick films are prepared by repeated cycles of sputtering and annealing. Annealing bulk samples at 1100 K results in small terraces with rounded ledges and steps with predominantly one O-Ce-O triple layer height while annealing at 1200 K produces well-ordered straight step edges in a hexagonal motif and step bunching. The morphology and topographic details of films are similar, however, films are destroyed upon heating above 1100 K. NC-AFM and KPFM images exhibit uniform and atomically perfect terraces on a single crystal surface while films exhibit significant inhomogeneities even for best possible preparation conditions. Applying X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS), a significant contamination of the bulk ceria sample with fluorine within the first 5 nm below the surface is found while a possible fluorine contamination of films is below the detection limits. After deposition of gold, a surprisingly strong interaction of gold adatoms to the (111) surface of bulk ceria is found. The pinning of individual adatoms to one specific surface site and the stability against sintering for annealing temperatures up to 520 K is discussed considering the fluorine contamination of bulk ceria samples. Additionally nanoscale gold clusters supported on ceria are fully characterized by employing elaborate NC-AFM and KPFM experiments gaining detailed information on their shape, crystalinity, epitaxy and binding to the substrate.

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Dans cette thèse, on s'intéresse à l'étude d'existence de solutions pour les processus de rafle. Ce problème prend la forme d'une inclusion différentielle contrainte avec des cônes normaux qui apparaissent naturellement dans nombreuses applications telles que le mouvement de foule, l'élastoplasticité, les mécaniques, les circuits électroniques, etc. L'objective de ce travail est de rapprocher deux importantes classes d'inclusions différentielles. D'une part, nous établissons quelques résultats d'existence de tube-solutions pour des processus de rafle à des ensembles uniformément prox-réguliers. D'autre part, nous présentons des résultats d'existence de solutions monotone par rapport à un préordre pour un système mixte d'inclusions différentielles projetées. De plus, nous montrons l'existence d'un point-selle pour notre système et nous fournissons deux exemples d'applications. / In this thesis, we were interested in the study of the existence of solutions for sweeping processes. This problem takes the form of a constrained differential inclusion involving normal cones which appears naturally in many applications such as crowd motion, elastoplasticity, mechanics, electrical circuit, etc.The aim of this work is to bring together two classes of differential inclusions. On one hand, we establish some existence results of solutions-tube for sweeping processes with uniformly prox-regular sets. On the other hand, we present existence results of monotone solutions with respect to a preorder for a mixed system of projected differential inclusions. In addition, we show that our system has a saddle-point and we provide two examples of applications.

Os materiais nanoestruturados vêm sendo extensivamente estudados, não somente pelas novas propriedades e suas possíveis aplicações tecnológicas, mas também pela busca de uma melhor compreensão dos aspectos físicos e químicos causados por suas reduzidas dimensões. A céria (CeO2) tem despertado grande interesse nas últimas décadas, pois tem papel vital em tecnologias emergentes para aplicações em setores que vão desde a área ambiental através do desenvolvimento de novos catalisadores, passando pela área energética com o desenvolvimento de células de combustível em estado sólido e em novas tecnologias como a spintrônica por meio do desenvolvimento de novos materiais, os óxidos magnéticos diluídos. As propriedades físico-químicas da céria são diretamente dependentes do método de síntese e da morfologia das partículas. Nesse contexto, esse trabalho teve como objetivo realizar a síntese através dos métodos dos precursores poliméricos e hidrotérmico assistido por micro-ondas e a caracterização físico-química de nanopartículas do sistema Ce(1-x)MxO2 (M = Cu, Co). Ensaios catalíticos destes pós foram realizados para verificar sua eficácia como catalisadores na reação de oxidação preferencial de monóxido de carbono, e na produção de hidrogênio através da reforma a vapor de etanol. As amostras foram caracterizadas por difração de raios X, espectroscopia UV-Visível, EPR, Raman e fotoluminescência, BET, microscopia eletrônica de varredura e transmissão e TPR. As amostras sintetizadas pelo método dos precursores poliméricos são constituídas por nanopartículas com tamanho da ordem de 30 nm, enquanto que as amostras sintetizadas pelo método hidrotérmico assistido por micro-ondas são constituídas por nanobastões com tamanho da ordem de 10 nm de diâmetro por 70 nm de comprimento. Dentre as amostras sintetizadas pelo método dos precursores poliméricos, o catalisador Ce0,97Cu0,03O2 foi o que apresentou o melhor resultado na conversão do CO (100%)(CO-PROX), e o catalisador Ce0,80Co0,20O2 apresentou 100% de conversão de etanol. Para as amostras sintetizadas pelo método hidrotérmico assistido por micro-ondas o catalisador Ce0,97Cu0,03O2 foi o que apresentou o melhor resultado na conversão do CO (85%)(CO-PROX), e todos os catalisadores com cobalto apresentaram 100% de conversão de etanol. As caracterizações físico-químicas revelaram que diferentes espécies de cobre/cobalto presentes nos catalisadores, o teor de cobre/cobalto presente e as interações entre o cobre/cobalto e o suporte de CeO2 são os fatores que mais contribuem na eficiência dos catalisadores. / Nanostructured materials have been extensively studied, not only by new properties and their possible technological applications, but also by the search for a better understanding of the physical and chemical aspects caused by its small size. Ceria (CeO2) have attracted great interest in recent decades, because it plays a vital role in emerging technologies for applications in sectors ranging from environmental area through the development of new catalysts, passing by the energy area with the development of solid state fuel cells and in new technologies such as spintronics through the development of new materials, the diluted magnetic oxides. The physico-chemical properties of ceria are directly dependent on the synthesis method and the morphology of the particles. In this context, this study aimed the synthesis via polymeric precursors and microwave-assisted hydrothermal methods and the physico-chemical characterization of nanoparticles from the Ce(1-x)MxO2 (M = Cu, Co) system. Catalytic tests of the powders were carried out to verify its efficiency as catalysts on carbon monoxide preferential oxidation reaction, and hydrogen production by steam reforming of ethanol. The samples were characterized by X-ray diffraction, UV-visible, EPR, Raman and photoluminescence spectroscopies, BET, scanning and transmission electron microscopy and TPR. Samples synthesized by polymeric precursors method consist of nanoparticles with sizes of about 30 nm, while the samples synthesized by microwave-assisted hydrothermal method consist of nanorods with 10 nm average diameter and 70 nm length. Among the samples synthesized by the polymeric precursors method, Ce0,97Cu0,03O2 was the one that presented the best result in the CO conversion (100%)(CO-PROX), and the Ce0,80Co0,20O2 catalyst presented 100% of ethanol conversion. For samples synthesized by microwave-assisted hydrothermal method the Ce0,97Cu0,03O2 catalyst was the one that presented the best result in the CO conversion (85%) (CO-PROX), and all catalysts with cobalt presented 100% of ethanol conversion. The physical-chemical characterizations revealed that different species of copper/cobalt present in the catalysts, the copper/cobalt content and interactions between copper/cobalt and the CeO2 support are the main factors that contribute on the efficiency of the catalysts.

Os materiais nanoestruturados vêm sendo extensivamente estudados, não somente pelas novas propriedades e suas possíveis aplicações tecnológicas, mas também pela busca de uma melhor compreensão dos aspectos físicos e químicos causados por suas reduzidas dimensões. A céria (CeO2) tem despertado grande interesse nas últimas décadas, pois tem papel vital em tecnologias emergentes para aplicações em setores que vão desde a área ambiental através do desenvolvimento de novos catalisadores, passando pela área energética com o desenvolvimento de células de combustível em estado sólido e em novas tecnologias como a spintrônica por meio do desenvolvimento de novos materiais, os óxidos magnéticos diluídos. As propriedades físico-químicas da céria são diretamente dependentes do método de síntese e da morfologia das partículas. Nesse contexto, esse trabalho teve como objetivo realizar a síntese através dos métodos dos precursores poliméricos e hidrotérmico assistido por micro-ondas e a caracterização físico-química de nanopartículas do sistema Ce(1-x)MxO2 (M = Cu, Co). Ensaios catalíticos destes pós foram realizados para verificar sua eficácia como catalisadores na reação de oxidação preferencial de monóxido de carbono, e na produção de hidrogênio através da reforma a vapor de etanol. As amostras foram caracterizadas por difração de raios X, espectroscopia UV-Visível, EPR, Raman e fotoluminescência, BET, microscopia eletrônica de varredura e transmissão e TPR. As amostras sintetizadas pelo método dos precursores poliméricos são constituídas por nanopartículas com tamanho da ordem de 30 nm, enquanto que as amostras sintetizadas pelo método hidrotérmico assistido por micro-ondas são constituídas por nanobastões com tamanho da ordem de 10 nm de diâmetro por 70 nm de comprimento. Dentre as amostras sintetizadas pelo método dos precursores poliméricos, o catalisador Ce0,97Cu0,03O2 foi o que apresentou o melhor resultado na conversão do CO (100%)(CO-PROX), e o catalisador Ce0,80Co0,20O2 apresentou 100% de conversão de etanol. Para as amostras sintetizadas pelo método hidrotérmico assistido por micro-ondas o catalisador Ce0,97Cu0,03O2 foi o que apresentou o melhor resultado na conversão do CO (85%)(CO-PROX), e todos os catalisadores com cobalto apresentaram 100% de conversão de etanol. As caracterizações físico-químicas revelaram que diferentes espécies de cobre/cobalto presentes nos catalisadores, o teor de cobre/cobalto presente e as interações entre o cobre/cobalto e o suporte de CeO2 são os fatores que mais contribuem na eficiência dos catalisadores. / Nanostructured materials have been extensively studied, not only by new properties and their possible technological applications, but also by the search for a better understanding of the physical and chemical aspects caused by its small size. Ceria (CeO2) have attracted great interest in recent decades, because it plays a vital role in emerging technologies for applications in sectors ranging from environmental area through the development of new catalysts, passing by the energy area with the development of solid state fuel cells and in new technologies such as spintronics through the development of new materials, the diluted magnetic oxides. The physico-chemical properties of ceria are directly dependent on the synthesis method and the morphology of the particles. In this context, this study aimed the synthesis via polymeric precursors and microwave-assisted hydrothermal methods and the physico-chemical characterization of nanoparticles from the Ce(1-x)MxO2 (M = Cu, Co) system. Catalytic tests of the powders were carried out to verify its efficiency as catalysts on carbon monoxide preferential oxidation reaction, and hydrogen production by steam reforming of ethanol. The samples were characterized by X-ray diffraction, UV-visible, EPR, Raman and photoluminescence spectroscopies, BET, scanning and transmission electron microscopy and TPR. Samples synthesized by polymeric precursors method consist of nanoparticles with sizes of about 30 nm, while the samples synthesized by microwave-assisted hydrothermal method consist of nanorods with 10 nm average diameter and 70 nm length. Among the samples synthesized by the polymeric precursors method, Ce0,97Cu0,03O2 was the one that presented the best result in the CO conversion (100%)(CO-PROX), and the Ce0,80Co0,20O2 catalyst presented 100% of ethanol conversion. For samples synthesized by microwave-assisted hydrothermal method the Ce0,97Cu0,03O2 catalyst was the one that presented the best result in the CO conversion (85%) (CO-PROX), and all catalysts with cobalt presented 100% of ethanol conversion. The physical-chemical characterizations revealed that different species of copper/cobalt present in the catalysts, the copper/cobalt content and interactions between copper/cobalt and the CeO2 support are the main factors that contribute on the efficiency of the catalysts.

Dans cette thèse de doctorat, nous apportons quelques contributions à la stabilité de Lyapunov non-régulière des inclusions différentielles de premier ordre avec opérateurs monotones maximaux, dans un cadre Hilbertien de dimension infini. Nous fournissons des caractérisations explicites, primales et/ou duales, des paires de Lyapunov faibles et fortes, dont les fonctions sont semi-continues inférieurement à valeurs réelles étendues, et associées à des inclusions différentielles dont la partie de droite est gouvernée par des perturbations Lipschitziennes des opérateurs dits Cusco F, ou des opérateurs monotones maximaux A, ou les deux à la fois x(t) ∈ F(x(t}} A(x(t}} t ≥ 0, x(0) ∈ domA. De manière équivalente, nous étudions l'invariance faible et forte des ensembles fermés pour ces inclusions différentielles. Comme dans L'approche classique de Lyapunov à la stabilité des équations différentielles, les résultats présentés dans cette thèse n'utilisent que les données du système différentiel; c'est-à-dire, l'opérateur A et la multifonction F, et donc pas besoin de connaître les solutions, ni les semi-groupes générés par les opérateurs monotones en question. Parce que les paires de Lyapunov sont formées par des fonctions qui sont simplement semi-continues inférieurement, et les ensembles invariants ne sont que ensembles fermés, nous faisons usage dans cette thèse à des outils de l'analyse non-lisse, afin de fournir des critères du premier ordre, utilisant des sous-différentiels généraux et des cônes normaux. Nous fournissons une analyse similaire pour les inclusions différentielles gouvernées par le cône normal proximal à des ensembles prox-réguliers. Notre analyse ci-dessus, nous a permis de présenter ces systèmes prox-réguliers d’apparence plus générale, comme des inclusions différentielles avec opérateurs monotones maximaux. Nous utilisons aussi nos résultats pour étudier la géométrie des opérateurs monotones maximaux, et plus précisément, la caractérisation de la frontière des valeurs de ces opérateurs seulement au moyen des valeurs situées à proximité, distinctes du point de référence. Ce résultat a des applications dans la stabilité des problèmes de la programmation semi-infinie. Nous utilisons également nos résultats sur les paires de Lyapunov et les ensembles invariants pour établir une étude systématique des observateurs de type Luenberger pour des inclusions différentielles avec des cônes normaux à des ensembles prox-réguliers. / In this PhD thesis, we make some contributions to nonsmooth Lyapunov stability of first-order differential inclusions with maximal monotone operators, in the setting of infinite-dimensional Hilbert spaces. We provide primal and dual explicit characterizations for parameterized weak and strong Lyapunov pairs of lower semicontinuous extended-real-valued functions, referred to as a-Lyapunov pairs, associated to differential inclusions with right-hand-sides governed by Lipschitz or Cusco perturbationsF of maximal monotone operators A, x(t) ∈ F(x(t}} A(x(t}} t ≥ 0, x(0) ∈ domA. Equivalently, we study the weak and strong invariance of sets with respect to such differential inclusions. As in the classical Lyapunov approach to the stability of differential equations, the presented results make use of only the data of the differential system; that is, the operator A and the multifunction F, and so no need to know about the solutions, nor the semi-groups generated by the monotone operators. Because our Lyapunov pairs and invariant sets candidates are just lower semicontinuous and closed, respectively, we make use of nonsmooth analysis to provide first-order-like criteria using general subdifferentials and normal cones. We provide similar analysis to non-convex differential inclusions governed by proximal normal cones to prox-regular sets. Our analysis above allowed to prove that such apparently more general systems can be easily coined into our convex setting. We also use our results to study the geometry of maximal monotone operators, and specifically, the characterization of the boundary of the values of such operators by means only of the values at nearby points, which are distinct of the reference point. This result has its application in the stability of semi-infinite programming problems. We also use our results on Lyapunov pairs and invariant sets to provide a systematic study of Luenberger-like observers design for differential inclusions with normal cones to prox-regular sets.

La réaction d’oxydation sélective du CO par O2 en présence d’un excès d’hydrogène (PROX) est considérée comme une étape de purification essentielle de l’H2 à utiliser dans des piles à combustible. L’objectif de cette thèse est de mieux comprendre le mécanisme de cette réaction sur des catalyseurs bimétallique s à base de Pt et Sn. Des catalyseurs modèles Pt et Pt-Sn ont été synthétisés en deux étapes : (i) formation de nanoparticules (NP) métalliques colloïdales en suspension suivi par ( ii) l’imprégnation de ces particules sur des supports. L’adsorption du CO suivit par spectroscopie FT-IR en réflexion diffuse (DRIFTS) a été utilisée pour caractériser ces solides après une réduction permettant de reformer des phases d’alliage PtSn. L’analyse DRIFTS permet de caractériser la nature des sites de Pt présents, soit dans l’alliage, soit dans des phases pures de Pt. La chaleur d’adsorption du CO sur la phase d’alliage a été mesurée par DRIFTS, pour la première fois, et apparait bien plus faible que celle sur le Pt seul. De manière surprenante, la ségrégation de l’alliage en présence de CO/H 2 à des températures inférieur es à 175°C a été mise en évidence. Des mesures in situ DRIFTS de la réaction d’oxydation préférentielle du CO (PROX) indiquent que l’alliage se transforme rapidement en Pt et SnOx de par la présence de l’O2. Aucune indication de la présence d’alliage n’a jamais pu être obtenue sous PROX, indiquant que les meilleures propriétés catalytiques associés aux phases Pt-Sn sont dues à leur habilité à générer une nouvelle phase active Pt+SnOx lors de leur ségrégation. Un modèle microcinétique du PROX sur Pt+SnOx a été développé sur la base de ceux pertinents à l’oxydation du CO et PROX sur Pt seul, permettant une modélisation satisfaisante des données. Ce travail montre l’intérêt du couplage des méthodes spectroscopiques et cinétiques pour la compréhension de la structure des catalyseurs « au travail » et des mécanismes de réactions complexes / The selective oxidation of CO in the presence of a large excess of H2 (PROX) is considered as a crucial step in the purification of H 2 to be used in low-temperature fuel cells, which are clean sources of energy. The objective of this thesis was to better understand the reaction mechanisms taking place over promising catalysts based on Pt and Sn. Model Pt-Sn catalysts were prepared by a two-step method: (i) synthesis of metallic nanoparticules (NP) in a colloidal suspension followed by (ii) the deposition of these NPs onto a support. The first step of the method enabled to produce well-controlled Pt-Sn NPs in terms of size and composition. However, the NPs were partly destroyed during the deposition step followed by calcination, due to the reoxidation of Sn. The adsorption of CO followed by diffuse reflectance spectroscopy (DRIFTS) was used to characterize the nature of these solids following a reduction, which was able to regenerate an alloyed phase. The DRIFTS analysis enabled to discriminate between Pt in an alloyed phase and Pt on monometallic surfaces. The heat of CO adsorption measured by DRIFTS appeared to be much lower than that associated with the pure Pt phase. Surprinsingly, a segregation of Pt and Sn was observed under a CO/H2 mixture below 175°C. In situ analysis by DRIFTS of the PROX reaction indicated that the Pt-Sn alloy rapidly decomposed in the presence of O2, forming an intimate mixture of Pt and SnOx. No evidence of the presence of Pt -Sn alloyed phases could be obtained under PROX conditions, suggesting that the superior catalytic activity of the Pt –Sn materials were related to the Pt+SnOx mixture. A detailed PROX microkinetic model was developed over Pt+SnOx, based on those relevant to CO oxidation and PROX over pure Pt. This work epitomises the benefits in combining in situ spectroscopic study with kinetic modelling to better understand the structure of catalysts “at work” and reaction mechanisms

Les propriétés des ensembles localement prox-réguliers ont été étudiées par R.A. Poliquin, R.T. Rockafellar et L. Thibault. Le concept de fonction ''primal lower nice'' a été introduit en dimension finie par R.A. Poliquin et étendu au cadre Hilbertien par A.B. Levy, R.A. Poliquin et L. Thibault. Dans cette thèse, la première partie est consacrée à une étude des outils et des objets géométriques de l'Analyse non lisse tels que les fonctions primal lower nice et les ensembles localement prox-réguliers. On donnera une définition quantifiée de la prox-régularité locale. La deuxième partie établit des résultats d'existence et d'unicité de solutions d'inéquations variationnelles se présentant sous forme d'inclusions différentielles associées au cône normal d'un ensemble localement prox-régulier. / The properties of locally prox-regular sets have been studied by R.A. Poliquin, R.T. Rockafellar and L. Thibault. R.A. Poliquin also introduced the concept of ``primal lower nice function. This dissertation is devoted, on one hand to the study of primal lower nice functions and locally prox-regular sets and, on the other hand, to show existence and uniqueness of solutions of differential variational inequalities involwing such sets. Concerning the first part, we introduce a quantified viewpoint of local-prox-regularity and establish a series of characterizations for set satisfying this property. In the second part, we study differential variational inequalities with locally prox-regular sets and we show the relevance of our quantified viewpoint to prove existence results of solutions.

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