No description available.

No description available.

The dissertation consists of the following three sections: 1. Hydroxyapatite (HA) coatings. In this work, we deposited HA precursor films from weak basic electrolytic solution (pH= 8-9) via an electrochemical approach; the deposits were changed into crystallite coatings of hydroxyapatite by sintering at specific temperatures (600-800 ºC). The formed coatings were mainly characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). XRD patterns show well-defined peaks of HA when sintered under vacuum conditions. FTIR measurements indicate the existence of hydroxyl groups, which were confirmed by the characteristic intensity of the stretching and bending bands at ~3575 and ~630 cm-1, respectively. The SEM shows an adhesive, crack free morphology for the double-layer coating surface of the samples sintered in a vacuum furnace. 2. Silver/polymer/clay nanocomposites. Silver nanoparticles were prepared in layered clay mineral (montmorillonite)/polymer (PVP: poly (vinyl pyrrolidone)) suspension by an electrochemical approach. The silver particles formed in the bulk suspension were stabilized by the PVP and partially exfoliated clay platelets, which acted as protective colloids to prevent coagulation of silver nanoparticles together. The synthesized silver nanoparticles/montmorillonite/PVP composite was characterized and identified by XRD, SEM, and TEM (transmission electron microscopy) measurements. 3. Ce-doped lead zirconate titanate (PZT) thin films. In this study, we fabricated cerium-doped PZT films (molar ratio of Zr/Ti:: 0.5:0.5) via cathodic electrodeposition on the indium tin oxide ( ITO) coated glass substrate. In the preparation process, the PZT films were modified by adding a small amount of cerium dopants, which led to the formation of Ce-doped PZT films after sintering at high temperatures. The fabricated PZT films on the ITO coated glass substrate may be used as electro-optic devices in the industrial application.

Hexaferrites have a broad scope for application based on their physical properties. To study the influence of replacing cerium and gadolinium ions in hexaferrites, it is very important to understand their structural, electrical, and magnetic properties of hexaferrites. In this regard, the W-type strontium hexaferrite doped with Ce3 + and Gd3+ ions was prepared using a proteic sol-gel process under a pressure of 3000 psi and sintered at 1200º C for 2 h at a heating rate of 1 and 2º C/min. A pure W-type strontium hexaferrite was identified using X-ray diffraction (XRD); the XRD patterns exhibited increasing lattice parameters and unit cell volume as a function of doping. Scanning electron microscopy analysis indicated growth on plates with hexagonal divisions. The inserted Gd3+ and Ce3+ ions caused imbalance in the lattice. Therefore, some of the Fe3+ ions present in the octahedral site were converted to Fe2+ ions. Thus, the Curie temperature was reduced to 474º C, increasing the coercivity and reducing the superexchange interactions between Fe-O. The high saturation magnetization and low coercivity in the samples indicate that the hexaferrites are potential candidates for applications involving microwave absorption. In addition, impedance spectroscopy measurements indicated the presence of a replacement threshold with rare earth ions, which results in an increased resistivity; this is predominantly mediated by oxygen vacancies in the Ce3+-doped hexaferrite. / As hexaferritas apresentam um vasto campo de aplicações a depender de suas propriedades físicas. Estudar a influência da substituição dos íons de cério e gadolínio é de suma importância para entender como funciona o mecanismo de obtenção das propriedades estruturais, elétricas e magnéticas nas hexaferritas. Dessa forma, a hexaferrita de estrôncio tipo W foi dopada com íons de Ce3+ e Gd3+ foi obtida via processo sol-gel proteico à 3000 psi e sinterizada a 1200º C/2h com taxa de aquecimento de 1 e 2 /C/min. A fase pura da hexaferrita de estrôncio tipo W foi identificada por difração de raios X com aumento dos parâmetros de rede e volume da cela unitária em função da dopagem. As análises de microscopia eletrônica de varredura indicam o crescimento em placas com clivagens hexagonais. . Os íons de Gd3+ e Ce3+ quando inseridos provocou um desbalanceamento de cargas, levando a transformação de certa quantidade de íons Fe3+, presente no sítio octaédrico, para Fe2+. Tal fato leva a redução da temperatura de Curie para 474º C, aumento da coercividade e redução das interações de super troca entre Fe-O. A alta magnetização de saturação e baixa coercividade apresentadas pelas amostras, indicam que as hexaferritas são considerados candidatos em potencial para fins de absorção de micro-ondas. Além disso, as medidas de espectroscopia de impedância indicam que existe um limiar de substituição com os íons terra rara para que haja aumento da resistividade e a condução ocorra predominantemente mediada por vacâncias de oxigênio na hexaferrita dopada com íon de Ce3+. Palavras

This dissertation focuses on the assessment and development of heterogeneous catalysts for the deperoxidation of cyclohexyl hydroperoxide and oxidation of cyclohexane, which will be based in metal oxides and gold nanoparticles. For this endeavour a multidisciplinary approach will be used combining theoretical chemistry, kinetic studies and synthesis and characterisation of materials. The starting choice for the catalyst to carry out the process is supported gold nanoparticles. The approach of this dissertation is to first model the mecha- nism of cyclohexyl hydroperoxide decomposition and oxidation of cyclohexane on gold nanoparticles by theoretical calculations, and use these findings to synthesise efficient heterogeneous catalysts which will be subsequently tested and optimised experimentally. But as it will be seen, some metal oxides are active rather than acting as mere supports, which will also be studied both theoretical and experimentally. Each chapter has a specific focus and constitutes a strand of the overall goal: Chapter 1 provides an introductory background on the topics that this dissertation lies upon: oxidation of cyclohexane, heterogeneous catalysis and catalysis by gold and metal oxides. Chapter 2 outlines the objectives of the thesis, formulating the relevant hypotheses of this research and the subsequent validation tests. Chapter 3 exposes the methodology with a brief conceptual background that has been used to carry out this work. Chapter 4 is the first chapter dealing with results. It consists in a theoretical study using density functional theory of the reaction mechanism over different models of gold nanoparticles, in order to study the influence of several parameters on their catalytic activity: the particle size, atom coordination, and presence of additional species like oxygen atoms and water. Chapter 5 uses the findings found in chapter 4 to drive the synthesis of supported gold nanoparticles. It consists in a experimental study of gold-based catalysts, which is combined with a theoretical study which takes into account an additional variable: the support. Chapter 6 exploits one of the findings of chapter 5. One of the supports used for anchoring the gold nanoparticles is active by itself, namely cerium oxide. This chapter comprises an experimental work about its activity, studying parameters like particle size, morphology and the effect of doping. Chapter 7 continues with the catalytic activity of cerium oxide-based materials, but now from a theoretical point of view. It first presents a systematic study of the parameters relevant for the proper quantum mechanical description of cerium oxide, which is followed by a mechanistic study on different models. Chapter 8 outlines the conclusions obtained in this dissertation, present- ing them in a summarised way. Even though each chapter presents its corresponding conclusions at its end, this chapter groups them all in a structured way for the reader's convenience, so a global view of the project can be swiftly grasped. The results herein further the knowledge of heterogeneous catalysis for the oxidation of cyclohexane, one of the most important industrial reactions, and which continues to be a challenge. Although the ultimate goal is to develop an industrial catalyst, the dissertation also aims to show how computational chemistry can drive the design of novel materials, and how it can help to understand catalytic reactions at the atomic level. / El presente trabajo se centra en el estudio y desarrollo de catalizadores heterogéneos para la desperoxidación de ciclohexil hidroperóxido y la oxidación de ciclohexano, basados en óxidos metálicos y nanopartículas de Au. Para lograr tal objetivo se ha usado un enfoque multidisciplinar, que combina química teórica y estudios cinéticos, a la vez que síntesis y caracterización de materiales. El candidato inicial para llevar a cabo el proceso consiste en partículas de Au soportadas. El camino a seguir pasa primero por modelizar el mecanismo de descomposición de ciclohexil hidroperóxido y oxidación de ciclohexano mediante cálculos teóricos, y utilizar el conocimiento generado por este estudio para dictar la síntesis de catalizadores heterogéneos, comprobando y optimizando posteriormente su actividad de forma experimental. Sin embargo, como será visto a lo largo de este trabajo, algunos óxidos metálicos dejan de lado su papel como mero soporte físico para las partículas de Au y son activos por sí mismos. Tal hecho será estudiado tanto teórica como experimentalmente. Cada capítulo tiene un objetivo específico, y es a su vez una parte del objetivo global de esta investigación: El capítulo 1 provee al lector de una breve introducción a los temas sobre los que yace este trabajo: oxidación de ciclohexano, catálisis heterogénea y catálisis mediante Au y óxidos metálicos. El capítulo 2 expone de una forma breve y concisa los objetivos de esta investigación, formulando la hipótesis de partida y los correspondientes experimentos para su validación. El capítulo 3 describe la metodología utilizada junto a una explicación de los fundamentos en los que se basa cada técnica. El capítulo 4 es el primer capítulo que discute los resultados obtenidos en esta investigación. Se trata de un estudio usando la teoria del funcional de densidad para investigar el mecanismo de reacción del proceso sobre diferentes modelos teóricos de Au, con el objetivo de comprender la influencia de diversos factores en la actividad catalítica, tales como el tamaño de partícula, la coordinación de los á'tomos de Au y la presencia de especies adicionales como átomos de O y agua. El capítulo 5 hace uso de los resultados obtenidos en el estudio anterior, y los utiliza para dirigir la síntesis de nanopartículas soportadas de Au. Se trata de un estudio experimental en el que se investigan diversos factores que pueden afectar a su actividad catalítica. Este estudio se combina a su vez con uno de tipo teórico en el que se tiene en cuenta la influencia del soporte en la actividad catalítica de las particulas de Au. El capítulo 6 se basa en uno de los resultados obtenidos en el capítulo 5. Uno de los soportes utilizados para anclar las partículas de Au resulta de por sí activo: el CeO2. Su notable actividad para catalizar este proceso exige un estudio en mayor profundidad, el cual se lleva a cabo en este capítulo. Parámetros como el tamaño de particula, la morfología de superficie y el dopaje entre otros se investigan en este punto. El capítulo 7 sigue la estela del trabajo anterior sobre CeO2, pero ahora desde el punto de vista de la química teórica. Presenta primero un estudio sistemático de parámetros relacionados con la mecánica cuá'ntica que afectan al CeO2, con el objetivo de alcanzar una descripción satisfactoria de los modelos teóricos para este óxido. Tras esto, se lleva a cabo un estudio del mecanismo de reacción en dichos modelos de CeO2, a fin de comprender el origen de su actividad catalítica. El capítulo 8 presenta de forma estructurada y concisa todas las conclusiones que se han sacado a raíz de los resultados obtenidos. Aún a pesar de que cada capítulo presenta sus correspondientes conclusiones al final, aquí se presentan de una forma agrupada a comodidad del lector, para que pueda obtener de forma ágil una visión global de los resultados de esta investigación. / Aquest treball es centra en l'estudi i desenvolupament de catalitzadors hetero- genis per a la desperoxidació de ciclohexil hidroperòxid i la oxidació de ciclohexà, basats en òxids metàl·lics i nanopartícules de Au. Per aconseguir aquest objectiu s'ha utilitzat un enfocament multidisciplinari, en el qual es combinen química teòrica i estudis cinètics amb síntesi i caracterització de materials. El candidat inicial per dur a terme el procés consisteix en partícules de Au suportades. El camí a seguir passa primer per modelitzar el mecanisme de descomposició del ciclohexil hidroperòxid i la oxidació de ciclohexà mitjançant càlculs teòrics, i utilitzar el coneixement generat per aquest estudi per dirigir la síntesi de catalitzadors heterogenis, comprovant i optimitzant posteriorment la seua activitat de forma experimental. No obstant això, com es veurà al llarg d'aquest treball, alguns òxids metàl·lics deixen de costat el seu paper com a suport físic de les partícules de Au y són actius per si mateixos. Aquest fet s'ha estudiat tant teòrica com experimentalment. Cada capítol té un objectiu específic i és al mateix temps una part de l'objectiu global d'aquesta recerca: El capítol 1 proporciona al lector una breu introducció als temes tractats en aquest treball: oxidació de ciclohexà, catàlisi heterogènia i catàlisi mitjançant Au i òxids metàl·lics. El capítol 2 exposa d'una forma breu i concisa els objectius d'aquesta investigació, formulant la hipòtesi inicial i els corresponents experiments per a la seua validació. El capítol 3 descriu la metodologia utilitzada conjuntament amb una explicació dels fonaments en els quals es basa cada tècnica. El capítol 4 és el primer capítol que discuteix els resultats obtinguts en aquesta investigació. Es tracta d'un estudi usant la teoria del funcional de densitat per investigar el mecanisme de reacció del procés en diferents models teòrics de Au, amb l'objectiu de comprendre la influència en l'activitat catalítica de diversos factors, com ara la grandària de partícula, la coordinació dels àtoms de Au i la presencia d'espècies addicionals, com àtoms de O i aigua. El capítol 5 fa ús dels resultats obtinguts en l'estudi anterior, i els utilitza per dirigir la síntesi de nanopartícules suportades de Au. Es tracta d'un estudi experimental en el qual s'investiguen diversos factors que poden afectar a la seua activitat catalítica. Aquest estudi es combina amb un altre de caràcter teòric en el qual es té en compte la influència del suport en la activitat catalítica de les partícules de Au. El capítol 6 es basa en un dels resultats obtinguts en el capítol 5. Un dels suports utilitzats per fixar les partícules de Au resulta de per si actiu: el CeO2. La seua notable activitat per catalitzar aquest procés demana un estudi de major profunditat, el qual es duu a terme en aquest capítol. Paràmetres com la grandària de partícula, la morfologia de superfície i el dopatge, entre altres, s'investiguen en aquest punt. El capítol 7 continua l'estudi anterior sobre el CeO2, però ara des del punt de vista de la química teòrica. Presenta en primer lloc un es- tudi sistemàtic de paràmetres relacionats amb la mecànica quàntica que afecten al CeO2, amb l'objectiu d'aconseguir una descripció satisfactòria pels models teòrics d'aquest òxid. Després, es duu a terme un estudi del mecanisme de reacció en aquests models de CeO2, a fi de com- prendre l'origen de la seua activitat catalítica. El capítol 8 presenta de forma estructurada i concisa totes les conclusions que s'han extret arran dels resultats obtinguts. Encara que cada capí- tol presenta les seues corresponents conclusions al final, ací es presenten d'una forma agrupada per a la comoditat del lector, per què puga obtindre de forma àgil una visió global dels result d'una forma agrupada per a la comoditat del lector, per què puga obtindre de forma à / López Auséns, JT. (2016). From Quantum Mechanics to Catalysis: Studies on the oxidation of alkanes by gold and metal oxides [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/76806 / TESIS

This diploma thesis deals with cerium-based conversion coatings for aluminium alloys. At first the mechanism of protection of metals by inhibitory substances is described in the theoretical section. The next chapter is devoted to application of lanthanide salts as cathodic corrosion inhibitors. Then the characterization of alloy AA 2024 follows. The main part is dedicated to the growth mechanism of the cerium-based mixed conversion coating on the alloy AA 2024. Finally, the factors affecting the character and the quality of obtained coatings are commented. In the experimental part an influence of the thermal activation together with the activation by a hydrogen peroxide was observed. The created film was characterized using SEM and EDS. The level of corrosion protection was evaluated by the polarization resistance measurement. erized using SEM and EDS. The level of corrosion protection was evaluated by the polarization resistance measurement.

Cette thèse porte sur les applications optiques de films d’oxynitrures de silicium dopés cérium et co-dopés cérium-ytterbium élaborés par pulvérisation cathodique magnétron radiofréquence. Les paramètres de dépôt ont été optimisés afin d’obtenir une intense émission visible à l’œil nu des ions Ce3+ dans la matrice hôte SiOxNy. Il est démontré que le flux d’azote est un paramètre crucial pour obtenir cette émission. Nous avons montré aussi que les ions Ce3+ peuvent être incorporés en grande quantité dans cette matrice, sans clusterisations jusqu’à de très hautes températures de recuits (1200°C). Ces excellentes propriétés optiques ont mené à une première application : la tentative d’élaboration de DEL bleue. Les premiers résultats obtenus montrent une électroluminescence peu intense, mais restent encourageants pour une étude plus approfondie. La deuxième application étudiée est le développement de couches à conversion de fréquence basse pour augmenter le rendement des cellules solaires à base de silicium. En effet les cellules solaires sont limitées par le recouvrement du spectre solaire et la plage d’absorption de la cellule. L’élaboration de films SiOxNy co-dopés Ce/Yb pour convertir un photon ultra-violet (300-400 nm) en deux photons infra-rouges (980 nm) permet de passer outre la limite théorique des cellules solaires. Les systèmes élaborés montrent une émission des ions Yb3+ en présence d’ions Ce3+ dans la matrice hôte SiOxNy. Les ions Ce3+ permettent d’excités les ions Yb3+ sur une large gamme spectrale et le mécanisme de transfert d’énergie entre ces deux terres rares est détaillé. Un rendement de conversion de 185% est obtenu pour la plus forte concentration en ions Yb3+. Pour améliorer ce système, l'ajout de miroirs de Bragg entre la couche à conversion et le substrat de silicium, représentant la cellule solaire, a été étudié théoriquement. Leur but est double : maximiser le flux de photons ultraviolets piégé dans la couche à conversion de fréquence et transmettre un maximum de photons infrarouges, qui sont facilement absorbables, vers la cellule solaire. / This thesis is dedicated to cerium doped and cerium-ytterbium co doped oxynitride silicon films optical applications grown by radio frequency magnetron sputtering. Growth parameters have been optimized in order to obtain a strong cerium emission visible to the naked eye in the matrix host SiOxNy, especially the nitrogen flux has a dominant role. We showed that cerium ions have a high solubility without clustering at very high annealing temperature (1200°C). Those excellent properties lead to a first application: the elaboration of blue LED. First results show a weak electroluminescence signal but are still encouraging for further study. The second application is the elaboration of frequency conversion layers to increase the efficiency of Si based solar cell. Indeed solar cell are limited by the mismatch between the solar spectrum and the cell absorption range. The elaboration of Ce/Yb co doped SiOxNy films to convert a UV photon (300-400 nm) into two infrared photons (980 nm) allows to overcome the solar cell theoretical limit. Layers grown show an Yb3+ ion emission in presence of Ce3+ ions in the host matrix SiOxNy. Ce3+ ions sensitize Yb3+ ions on a large spectral range and their cooperative energy transfer mechanism is detailed. An efficiency of 185% is obtained for the higher dopants atomic concentration. In order to improve this system, the effect of adding Bragg mirrors placed between the conversion layer and the silicon substrate, which represents the solar cell, is theoretically studied. Their aim is double: increase the maximum flux of UV photons trapped in the frequency conversion layer and transmit a maximum of infrared photons, which are easily absorbable, toward the solar cell.

In this work ways of preparation of thin epitaxial cerium oxide film on Cu(110) surface were studied. X-ray photoelectron spectroscopy (XPS), X-ray photoelectron difraction (XPD), low energy electron difraction (LEED), ion scattering spectroscopy (ISS) and scanning tunneling microscopy (STM) were used for the characterization of prepared systems. The island structure of CeO2 was prepared by the method of reactive evaporation in oxygen atmosphere. The influence of temperature on the electronic structure and morphology was studied. At the temperature above 550 ˚C partial reduction to Ce2O3 and reordering of the islands to the CeO2(331) structure was observed. The ceria promoted oxidation of copper surface was approved, since the clean c(6x2) reconstruction of the surface was observed at the oxygen exposure 1,5 order of magnitude lower then on Cu(110) alone. The other model system was prepared by cerium evaporation to the oxygen precovered Cu(110) surface. The mix of (2x1) and c(6x2) surface reconstruction was formed by oxygen exposition at 300 ˚C. Cerium was deposited on this surface, also at 300 ˚C. During the following heating to 500 ˚C the formation of epitaxial film Ce2O3(0001) was observed, accompanied by the formation of large hundreds nm long smooth band structures in the [11̄0] direction.

Title: Study of new catalytic materials for proton exchange membrane fuel cells Author: Petr Homola Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. Abstract: Submitted thesis deals with study of thin layers based on platinum and cerium oxides in order to use them in fuel cells with polymer membrane (PEM- FC). A set of samples with different amount of platinum was prepared by means of magnetron sputtering. Samples were investigated by X - ray Photoelectron Spectroscopy (XPS) and results were confronted with sputtering parameters. It was found out that chemical state of platinum is related to its amount in thin layer. The less platinum was contained in thin layer, the less amount of Pt0 state was observed and amounts of Pt2+ and Pt4+ states increased. Furthermore the temperature stability of prepared layers in the interval from room temperature to 250 ◦ C was studied by means of XPS. The adsorption of carbon monoxide was measured by infrared absorption spectroscopy (IRAS). Increasing degree of adsorption on sample probably related to platinum reduction with increased tem- perature was observed. Measurements of other samples were devaluated by strong contamination with nickel carbonyls. Keywords: PEMFC, cerium oxide, magnetron sputtering, XPS, CO adsorption

Title: Study of CeOX / Rh inverse catalyst Author: Bc. Miroslav Kettner Department: Department of Surface and Plasma Science Supervisor: doc. RNDr. Václav Nehasil, Dr., Department of Surface and Plasma Science Abstract: Inverse catalysts of cerium oxide deposited on polycrystalline and monocrystalline (111) rhodium substrates were studied by means of surface science experimental methods. Growth characteristics of cerium oxide were investigated in dependence on deposition conditions and different thickness determination methods were compared. Acording to oxidizing or reducing exposition conditions changes in degree of oxidation of CeOX were observed. Further spectra analysis showed additional Ce-Rh alloy formation. Adsorption positions CO on-top and CO hollow on Rh (111) surface were differentiated by spectra fitting procedures. Oxygen absorption and reverse desorption in CeOX was confirmed. Performed experiments indicate that this process occurs through oxide-metal interface. CO oxidation reaction mechanisms at room temperature were proposed. Cerium oxide presence is necessary for reaction occurrence. Significant influence of deposited CeOX on proposed CO oxidation reaction mechanisms was proved by this way. Keywords: Rhodium, cerium oxide, alloy, inverse catalyst, CO oxidation.