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Innovative Design of Heterogeneous Catalysts with Improved CO2 Hydrogenation PerformanceCored Bandrés, Jorge 30 March 2023 (has links)
Tesis por compendio / [ES] El cambio climático es una de las amenazas de nuestro tiempo. Los gases de efecto invernadero, como el CO2, son los principales causantes de este fenómeno, siendo necesario disminuir urgentemente sus emisiones. En 2019, la Comisión Europa presentó el "Pacto Verde Europeo", que será clave para alcanzar un objetivo tremendamente ambicioso para nuestra región: la neutralidad climática de aquí a 2050. Las estrategias de descarbonización incluidas en su hoja de ruta van a implicar necesariamente la transición energética de los combustibles fósiles a las energías renovables, reduciendo de forma masiva la liberación de CO2. En este sentido, el desarrollo de tecnologías efectivas de Captura, Almacenamiento y Uso del Carbono (CAUC) permitirá la valorización del CO2, evolucionando hacia una economía de carbono circular.
La presente Tesis Doctoral se enmarca en el diseño, síntesis y caracterización de sistemas catalíticos heterogéneos innovadores basados en metales capaces de transformar el CO2 en otros productos de valor añadido. Entre un amplio catálogo de reacciones que "conectan" el CO2 con diversos compuestos basados en carbono, esta Tesis se centrará principalmente en la síntesis de dos moléculas C1 plataforma de interés industrial: el metanol y el metano.
Los Capítulos 3 y 4 están dedicados a la síntesis de metanol, un proceso exotérmico limitado termodinámicamente debido a la estabilidad inherente de la molécula de CO2, así como a la presencia de la reacción competitiva RWGS. Por un lado, el Capítulo 3 se centra en el efecto promotor del galio sobre las propiedades estructurales, electrónicas y catalíticas de materiales basados en Cu/ZnO (sistemas CZG). Mediante un enfoque espectroscópico-catalítico multidisciplinar se ha comparado el efecto promotor del Ga3+ dopado en la red de un ZnO tipo wurtzita presente en un catalizador Cu/ZnO/Ga2O3 con el de una fase de galato de zinc (ZnGa2O4). Por otro lado, en el Capítulo 4 se muestra un catalizador bifuncional que contiene nanopartículas de Cu de 2 nm y especies Cu+, con el objetivo de enfrentarse a la inherente baja actividad de estas pequeñas partículas, hecho que impide mejorar la eficiencia atómica de los catalizadores, dificultando así la obtención de resultados catalíticos competitivos en la hidrogenación de CO2. La realización de un estudio espectroscópico detallado (combinado con cálculo teórico y ensayos catalíticos) sobre un catalizador óxido mixto de Cu-Mg-Al derivado de un precursor de hidrotalcita tras calcinación y posterior reducción (CuHT-230) pone de manifiesto el papel clave de los iones Cu+ dopados en estructura en la producción de metanol.
El éxito de las tecnologías CAUC a medio-largo plazo dependerá no solo del desarrollo de catalizadores competitivos, sino también de su capacidad para operar en condiciones de reacción más suaves, permitiendo que estos procesos sean viables económicamente. Por ello, el concepto de eficiencia energética se abordará en el Capítulo 5, a través de un innovador diseño de catalizador tipo "shell/core" formado por un núcleo de rutenio metálico y una envoltura de carburo de rutenio, sintetizado via hidrotermal. Este sistema (Ru@EDTA-20) exhibe una actividad excepcionalmente alta para la hidrogenación de CO2 a metano a bajas temperaturas (160-200 °C) con una selectividad a CH4 del 100%, superando a catalizadores de bibliografía que normalmente operan a mayores temperaturas (400-500 °C).
Por último, en el Capítulo 6 se estudia un catalizador modelo compuesto por un alumino-silicato bidimensional sintetizado sobre una superficie de Ru(0001), investigación realizada durante mi estancia internacional en el Laboratorio Nacional de Brookhaven (Nueva York, EE.UU.). La combinación de estos materiales en el mismo composite permite la creación de un nanoespacio confinado que puede emplearse como nanorreactor. En este proyecto, se seleccionó la reacción de formación de agua como modelo, que se exploró a nivel fundamental en el sincrotrón NSLS-II. / [CA] El canvi climàtic és una de les amenaces del nostre temps. Els gasos d'efecte d'hivernacle, com el diòxid de carboni, són els principals causants d'aquest fenomen, sent necessari reduir urgentment les seues emissions. En 2019, la Comissió Europea va presentar el "Pacte Verd Europeu", que serà clau per a aconseguir un objectiu tremendament ambiciós per a la nostra regió: la neutralitat climàtica d'ací a 2050. Les estratègies de descarbonització incloses en el seu full de ruta implicaran necessàriament la transició energètica dels combustibles fòssils a les energies renovables, reduint de manera massiva l'alliberament de CO2. En aquest sentit, el desenvolupament de tecnologies efectives de Captura, Emmagatzematge i Ús del Carboni (CEUC) permetrà la valorització del CO2, evolucionant cap a una economia de carboni circular.
La present Tesi Doctoral s'emmarca en el disseny, síntesi i caracterització de sistemes catalítics heterogenis innovadors basats en metalls capaços de transformar el CO2 en altres productes de valor afegit. Entre un ampli catàleg de reaccions que "connecten" el CO2 amb diversos compostos basats en carboni, aquesta Tesi se centrarà principalment en la síntesi de dues molècules C1 plataforma d'interés industrial: el metanol i el metà.
Els Capítols 3 i 4 estan dedicats a la síntesi de metanol, un procés exotèrmic limitat degut tant a l'estabilitat inherent de la molècula de CO2 com a la presència de la reacció competitiva RWGS. D'una banda, el Capítol 3 se centra en l'efecte promotor del gal·li sobre les propietats estructurals, electròniques i catalítiques de materials basats en Cu/ZnO (sistemes CZG). Mitjançant un enfocament espectroscòpic-catalític multidisciplinari s'ha comparat l'efecte promotor del Ga3+ dopat en la xarxa d'un ZnO (wurtzita) present en un catalitzador Cu/ZnO/Ga2O3 amb el d'una fase de ZnGa2O4. D'altra banda, en el Capítol 4 es mostra un catalitzador bifuncional que conté nanopartícules de Cu de 2 nm i espècies Cu+, amb l'objectiu d'enfrontar-se a la inherent baixa activitat d'aquestes petites partícules, fet que impedeix millorar l'eficiència atòmica dels catalitzadors, dificultant així l'obtenció de resultats catalítics competitius en la hidrogenació de CO2. La realització d'un estudi espectroscòpic detallat (combinat amb càlcul teòric i assajos catalítics) sobre un catalitzador òxid mixt de Cu-Mg-Al derivat d'un precursor de hidrotalcita després de calcinació i posterior reducció (CuHT-230) posa de manifest el paper clau dels ions Cu+ dopats en estructura en la producció de metanol.
L'èxit de les tecnologies CEUC a mig-llarg termini dependrà no solament del desenvolupament de catalitzadors competitius, sinó també de la seua capacitat per a operar en condicions de reacció més suaus, permetent que aquests processos siguen viables econòmicament. Per això, el concepte d'eficiència energètica s'abordarà en el Capítol 5, a través un innovador disseny de catalitzador tipus "shell/core" format per un nucli de ruteni metàl·lic i un embolcall de carbur de ruteni, sintetitzat mitjançant tractament hidrotermal. Aquest sistema (Ru@EDTA-20) exhibeix una activitat excepcionalment alta per a la hidrogenació de CO2 a metà a baixes temperatures (160-200 °C) amb una selectivitat a CH4 del 100%, superant a catalitzadors de bibliografia que normalment operen a majors temperatures (400-500 °C).
Finalment, en el Capítol 6 s'estudia un catalitzador model compost per un alumino-silicat bidimensional sintetitzat sobre una superfície de Ru(0001), investigació realitzada durant la meua estada internacional en el Laboratori Nacional de Brookhaven (Nova York, els Estats Units). La combinació d'aquests dos materials en el mateix "composite" permet la creació d'un nano-espai confinat que pot emprar-se com nano-reactor. En aquest projecte, es va seleccionar la reacció de formació d'aigua com a model, que es va explorar a nivell fonamental en el sincrotró NSLS-II. / [EN] Climate change is one of the existential threats of our times. Greenhouse gases (GHG), such as carbon dioxide, are primary drivers of this phenomenon, and their emissions need to be urgently reduced. In 2019, the European Commission presented the European Green Deal, which will help the EU to attain an ambitious goal for our region: to become carbon-neutral by 2050. The decarbonization strategies included in the roadmap towards net-zero emissions will imply the energy transition from fossil fuels to renewable energies, with a massive reduction of CO2 deliverance. In this sense, the development of effective Carbon Capture and Storage (CCS) and Carbon Capture and Utilization (CCU) technologies will allow the valorization of CO2, evolving into a circular carbon economy.
The present Doctoral Thesis focuses on the design, synthesis and characterization of innovative heterogeneous metal-based systems, which are able to transform CO2 into value-added products. Among a wide catalogue of reactions that "connects" CO2 with various carbon-based compounds, this thesis will be devoted to the synthesis of two C1 platform chemicals of industrial interest: methanol and methane.
Chapters 3 and 4 are dedicated to methanol synthesis, a highly hampered exothermic process due to the inherent stability of the CO2 molecule and the presence of the competitive reverse water-gas shift reaction (RWSG). On the one hand, Chapter 3 is focused on the promoting effect of gallium on the structural, electronic, and catalytic properties of Cu/ZnO based materials (CZG systems). In particular, the promoting effect of Ga3+-doped in the wurtzite ZnO lattice of a Cu/ZnO/Ga2O3 catalyst is compared to that of a zinc gallate (ZnGa2O4) phase following a multimodal spectroscopic-catalytic approach. In Chapter 4, a bifunctional catalyst containing 2 nm Cu nanoparticles and Cu+ species is presented, to overcome the "assumed" low activity of small copper particles that prevents obtaining high atom efficiency and competitive catalytic results in the CO2 hydrogenation to methanol. A detailed spectroscopic study (combined with theoretical calculations and catalytic tests) performed on a Cu-Mg-Al mixed oxide catalyst derived from a hydrotalcite precursor by calcination and further reduction (CuHT-230) highlights the key role of doped Cu+ ions in methanol production.
The success of CCU technologies in the medium-long term will depend not only on the development of competitive catalysts but also on their ability to operate under milder reaction conditions, which will make these processes economically viable. Consequently, the energy efficiency issue will be addressed in Chapter 5 with the innovative design of a core-shell structure formed by a core of metallic ruthenium and a shell of ruthenium carbide, synthesized via hydrothermal treatment. This catalyst (Ru@EDTA-20) exhibits exceptional high activity for CO2 hydrogenation to methane (Sabatier reaction) at low temperatures (160-200 °C) with 100% selectivity to CH4, outperforming the state of the art catalysts operating at 400-500 °C.
Finally, Chapter 6 covers the investigation carried out on a model ruthenium-based catalyst composed of a 2D-bilayered aluminosilicate grown over a Ru(0001) surface during my international short-term stay at Brookhaven National Laboratory (New York, USA). The combination of these materials in a composite allows the creation of a confined nano-space that can be exploited as a nano-reactor. In this project, water formation reaction (WFR) was selected as model reaction, which was fundamentally explored at NSLS-II synchrotron. / Cored Bandrés, J. (2022). Innovative Design of Heterogeneous Catalysts with Improved CO2 Hydrogenation Performance [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/182403 / Compendio
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Physical chemical aspects of lanthanide-based nanoparticles: crystal structure, cation exchange, architecture, and ion distribution as well as their utilization as multifunctional nanoparticles.Dong, Cunhai 12 December 2011 (has links)
Lanthanide-based nanoparticles are of interest for optical displays, catalysis, telecommunication, bio-imaging, magnetic resonance imaging, multimodal imaging, etc. These applications are possible partly because the preparation of lanthanide-based nanoparticles has made tremendous progress. Now, nanoparticles are routinely being made with a good control over size, crystal phase and even shape. Despite the achievements, little attention is given to the fundamental physical chemistry aspects, such as crystal structure, architecture, cation exchange, etc. The results of the study on the crystal structures of LnF3 nanoparticles show that the middle GdF3 and EuF3 nanoparticles have two crystal phases, which has then been tuned by doping with La3+ ions. However, the required doping level is very different from the bulk. While the results for the bulk are well explained by thermodynamic calculations, kinetics is actually responsible for the results of the undoped and doped GdF3 and EuF3 nanoparticles. The attempt to make LnF3 core-shell nanoparticles led to the finding of cation exchange, a phenomenon that upon exposure of LnF3 nanoparticles to an aqueous solution containing Ln3+ ions, the Ln3+ ions in the nanoparticles are replaced by the Ln3+ ions in the solution. The consequence of the cation exchange is that LnF3 core-shell nanoparticles are unlikely to form in aqueous media using a core-shell synthesis procedure. It has also been verified that nanoparticles synthesized using an alloy procedure do not always have an alloy structure. This means that the core-shell and alloy structure of nanoparticles in the literature may not be true. The investigation of the architecture of nanoparticles synthesized in aqueous media is extended to those synthesized in organic media. The dopant ion distribution in NaGdF4 nanoparticles has been examined. It has been found that they don’t have the generally assumed statistical dopant distribution. Instead, they have a gradient structure with one type of Ln3+ ions more concentrated towards the center and the other type more concentrated towards the surface of the nanoparticles. With the understanding of these physical insights, lanthanide-based core-shell nanoparticles are prepared using the cation exchange. These core-shell nanoparticles containing a photoluminscent core and a paramagnetic shell are promising candidates for multimodal imaging. / Graduate
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Die autokatalytische H 2 O 2 -Reduktion an Ag-ElektrodenEickes, Christian 31 May 2001 (has links)
Es konnte vor kurzem gezeigt werden, daß die Reduktion von Wasserstoffperoxid (H2O2) an Silber in Perchlorsäure (HClO4) über zwei parallele Wege verläuft. Die normale Reduktion wird bei einer Überspannung von -1,5 V beobachtet, während die zweite Reduktionsreaktion bei einer deutlich geringeren Überspannung bei -1,0 V stattfindet. Im zweiten Reaktionsweg wird OHad als instabile Zwischenspezies gebildet und wirkt katalytisch auf die H2O2-Reduktion. Daher wird angenommen, daß die zweite Reaktion eine autokatalytische Reduktion ist. Diese autokatalytische Reaktion wird nach einer ge-wissen Zeit deaktiviert, die von der Rotationsgeschwindigkeit der Elektrode abhängig ist. Sie kann wiedererlangt werden, wenn die Elektrode negativ polarisiert wird. In dieser Arbeit wurden Ex-situ-XPS-Messungen an herausgezogenen Ag(111)-Elektroden durch-geführt. Die Analyse führt zu dem Ergebnis, daß die Deaktivierung durch geringe Chlorid-Verunreinigungen verursacht wird. Elektrochemische Impedanzspektren werden zusammen mit numerischen Simulationen der Faradayschen Impedanz des autokata-lytischen Bereiches gezeigt. Diese basieren auf Annahmen von kinetischen Geschwin-digkeitsgesetzen, die früher postuliert wurden. Die experimentellen Daten stimmen sehr gut mit den Ergebnissen der theoretischen Rechnungen überein. Dies unterstützt den angenommen autokatalytischen Mechanismus. / Recently, it was shown that the hydrogen peroxide (H2O2) reduction on silver in perchloric acid (HClO4) proceeds in two parallel paths. The normal reduction is observed at an overpotential of -1.5 V, whereas a second reduction reaction occurs at a significantly lower overpotential at -1.0 V. The second reaction involves the unstable intermediate OHad, which also acts as a catalyst. Hence, the second reaction has been proposed to be an autocatalytic one. This autocatalytic reaction is deactivated after a certain time that depends on the rotation speed of the electrode. It can be recovered if the electrode is negatively polarized. In this thesis work, ex-situ XPS measurements on emersed Ag(111) electrodes were conducted. The analysis leads to the conclusion that the deactivation is caused by a small amount of chloride contamination. Electrochemical impedance spectra are presented together with numerical simulations for the faradaic impedance in the autocatalytic region based on previously suggested kinetic rate laws. The experimental data fit well with the results of the theoretical calculations, which strongly supports the autocatalytic mechanism.
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Etude des interfaces de batteries lithium-ion : application aux anodes de conversion / Interfaces for conversion anodes - reliability and efficiency studiesZhang, Wanjie 02 December 2014 (has links)
Les matériaux dits de conversion à base de Sb et Sn, utilisés comme électrodes, apparaissent comme des composés particulièrement intéressants compte tenu de leur forte capacité théorique. Le matériau TiSnSb a été récemment développé en tant qu’électrode négative pour batteries lithium-ion. Ce matériau est capable d’accueilir, de façon réversible, 6,5 Li par unité formulaire, ce qui correspond à une capacité spécifique de 580 mAh/g. Dans le domaine des batteries lithium-ion, les propriétés de l’interface électrode/électrolyte (« solid electrolyte interphase », SEI), formant une couche de passivation protectrice à la surface des électrodes sont considérées comme essentielles pour les performances au sens large des batteries. Cet aspect représente le sujet majeur traité dans ce travail de thèse. Dans cet optique, nous avons tout d'abord étudié les propriétés électrochimiques de l'électrode TiSnSb sous divers aspects, dont les effets du régime de cyclage, l’influence de la nature des additifs au sein de l’électrolyte ainsi que l’utilisation de liquides ioniques à température ambiante (RTILs). En particulier, un système d'électrolyte à base de RTILs a été développé et optimisé vis-à-vis des performances électrochimiques. Afin de caractériser l’interface électrode-électrolyte, deux techniques de caractérisation majeures ont été utilisées : la Spectroscopie Photoélectronique à Rayonnement X (XPS) et la Spectroscopie d'Impédance électrochimique (EIS). Cette étude a permis de cibler certains paramètres essentiels liant les aspects performances électrochimiques à la nature de l’interface électrode-électrolyte. / In the past decades, the need for portable power has accelerated due to the miniaturization of electronic appliances. It continues to drive research and development of advanced energy systems, especially for lithium ion battery systems. As a consequence, conversion materials for lithium-ion batteries, including Sb and Sn-based compounds, have attracted much intense attention for their high storage capacities. Among conversion materials, TiSnSb has been recently developed as a negative electrode for lithium-ion batteries. This material is able to reversibly take up 6.5 Li per formula unit which corresponds to a specific capacity of 580 mAh/g. In the field of lithium-ion battery research, the solid electrolyte interphase (SEI) as a protective passivation film formed at electrode surface owing to the reduction of the electrolyte components, has been considered as a determinant factor on the performances of lithium-ion battery. Thus it has been a focused topic of many researches. However, little information can be found about the formation and composition of the SEI layer formed on TiSnSb conversion electrode at this time. With the aim to investigate the influences of the SEI layer on the performances of composite TiSnSb electrode, we first studied the electrochemical properties of the electrode from various aspects, including the effects of cycling rates, electrolyte additives, as well as room temperature ionic liquids (RTILs). Especially, a RTILs-based electrolyte system was developed and optimized by evaluating its physicochemical properties to be able to further improve the performances of TiSnSb electrode. In order to characterize the SEI layer formed at electrode surface, we performed X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). This study allowed to target some essential parameters concerning electrochemical performances linked with the nature of the solid electrolyte interphase.*
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Caractérisation de nanostructures de Fe élaborées sur substrat isolant LaAlO3 : expériences et simulation / Characterization of Fe nanostructures elaborate on insulator LaAlO3 : expérience and simulationZanouni, Mohamed 11 September 2015 (has links)
Les mémoires flash non volatiles - utilisées dans les ordinateurs, les téléphones portables ou les clés USB - peuvent être constituées de nanostructures semiconductrices (SC) ou métalliques insérées dans une matrice isolante. Elles nécessitent l’élaboration d’hétérostructures de type "oxyde/métal/oxyde/SC" et la maîtrise de chaque interface. Dans ce cadre, nous avons étudié les premiers stades de la croissance de nanostructures de Fer élaborées par épitaxie par jet moléculaire (EJM) sur les substrats d’oxyde (high-k) cristallins LaAlO3(001) et LaAlO3(111). Les propriétés chimiques et structurales ont été déterminées, in-situ, par spectroscopie de photoélectrons X (XPS), diffraction de photoélectrons X (XPD) et diffraction d’électrons (RHEED et LEED) puis ex-situ par microscopie électronique en transmission (TEM). Une étude par simulation des profils XPD, basée sur la théorie de la diffusion multiple, a été menée à l’aide du programme de calcul Ms-Spec. L’étude de la croissance de Fe sur LaAlO3(001) à différentes températures de substrat a montré l’existence d’une fenêtre étroite de température, autour de 500 °C, où la croissance de Fe est épitaxique et de type Volmer-Weber (îlots 3D). Les analyses RHEED, XPD et TEM ont mis en évidence une unique relation d’épitaxie, où la maille élémentaire de Fe est tournée de 45° par rapport à celle du substrat. Les résultats XPS ont montré un environnement chimique unique des atomes de Fer (forme atomique), traduisant l’absence de toute inter-diffusion à l’interface Fe/LaAlO3(001). L’étude de la croissance de Fe sur LaAlO3(111) a également mis en évidence un mode de croissance Volmer-Weber et une interface abrupte. Par ailleurs, tout un travail de développement à l'intérieur du code Ms-Spec a été nécessaire afin de surmonter des problèmes de convergence des calculs de diffusion multiple rencontrés dans le cas d’atomes lourds ayant des énergies cinétiques élevées (atomes de La dans LaAlO3). À cette fin, quatre hypothèses ont été formulés:1- Une prise en compte insuffisante des processus inélastiques :2- L’approximation muffin-tin n'est plus suffisante pour décrire correctement le potentiel ;3- Trop de chemins de faible intensité sont négligés ;4- Divergence de la série de diffusion multiple utilisée pour calculer la section efficace.Les calculs ont montré que les trois premières hypothèses n’ont pas d’influence sur la convergence dans le cas présent. En revanche, la quatrième hypothèse a été validée. En effet, on a montré que du fait du fort pouvoir diffuseur des atomes de La, le développement en série de diffusion multiple pouvait diverger (rayon spectral, i.e. la plus grande des valeurs propres en module de la matrice de diffusion, > 1) pour des grandes tailles d'amas de LaAlO3, alors qu’il converge pour des amas de Si et de MgO de taille similaire (les deux systèmes utilisés en comparaison). Par ailleurs, au-delà de quelques centaines d’atomes, le rayon spectral de LaAlO3, même inférieur à 1, reste important ce qui rend la convergence très lente. / Non-volatile flash memories embedding nanocrystals (NC) are promissing devices for use in computers, mobiles phones or USB keys. The insertion of semiconducting (SC) or metal NC in an insulating matrix requires the elaboration of complex "oxide/metal/oxide/SC" heterostructures and the control of the associated successive growth steps. In this context, we have studied the first growth stades of Fe nanostructures elaborated by Molecular Beam Epitaxy (MBE) on the of crystalline oxides (high-k) substrates of LaAlO3(001) and LaAlO3(111). Chemical and structural properties were investigated in-situ, by X-ray photoelectron spectroscopy (XPS), X-ray photoelectron diffraction (XPD) and electron diffraction (RHEED and LEED), and ex-situ by transmission electron spectroscopy (TEM). A simulation study of XPD profiles, based on the theory of multiple scattering, was conducted using the Ms-Spec calculation program. The study of the growth of Fe on LaAlO3(001) at different substrate temperatures showed the existence of a narrow temperature window, around 500 °C, where Fe has epitaxial growth with Volmer-Weber type (3D islands). The RHEED, XPD and TEM analysis showed a single epitaxial relationship, where the Fe unit cell is rotated by 45° compared to the substrate one. The XPS results showed a unique chemical environment of Fe atoms (atomic form), reflecting the absence of inter-diffusion in the Fe/LaAlO3(001) interface. The study of the Fe grown on LaAlO3(111) also showed a Volmer-Weber growth mode and an abrupt interface.Moreover, further development work within the Ms-Spec code was needed to overcome the issue of multiple scattering calculations convergence usually encountered in the case of heavy atoms with high kinetic energies (La atoms in the LaAlO3). In this regard, four hypotheses were formulated : 1- Insufficient consideration of the inelastic processes ;2- The muffin-tin approximation is no longer sufficient to adequately describe the potential ;3- Unduly low intensity paths are neglected ;4- Divergence of multile scattering series used to calculate the cross section.The calculations allowed us to rule out the first three hypothesis, since no influence on convergence was found in this case. However, the fourth hypothesis was validated. Indeed, it was shown that due to the high power diffuser of the La atoms, the multiple scattering series expansion could diverge (spectral radius, i.e. the largest eigenvalue modulus of the scattering matrix,> 1) for large sizes of LaAlO3 clusters. Whereas, it converges to the clusters of Si and MgO of similar size (both systems used in comparison). Furthermore, even less than 1, spectral radius of LaAlO3 remains important beyond few hundred atoms, thus rendering the convergence very slow.
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Thrombin inhibitors grafting on polyester membranes for the preparation of blood-compatible materialsSalvagnini, Claudio 28 November 2005 (has links)
The design of biomaterials, historically initiated and developed by physicians and engineers, in the last decades has slowly shifted toward a more biochemical based approach. For the replacement, repair and regeneration of tissues scientists are now focusing on materials that stimulate specific biological response at the molecular level. These biomaterials have already shown interesting applications in cell proliferation, differentiation, and extracellular matrix production and organization when the material modifications are designed to elicit specific interactions with cell integrins. In the present work we propose the application of this strategy for the development of blood-compatible materials. We first identified, in the coagulation cascade a key enzyme that constitute a valuable biological target for the development of anti-thrombogenic compounds. Piperazinyl-amide derivatives of N-alfa-(3-trifluoromethyl-benzenesulfonyl)-L-arginine were synthesized as graftable thrombin inhibitors. These inhibitors provided a spacer arm for surface grafting and a fluorine tag for XPS (X-ray photoelectron spectroscopy) detection. The possible disturbance of biological activity due to a variable spacer-arm fixed on the N-4 piperazinyl position was evaluated in vitro against human alfa-thrombin, in silico by molecular modelling and via X-ray diffraction study. Selected inhibitors, having inhibition potency in the mM range, were grafted on polyesters surface via wet chemistry and photochemical activation treatments. Wet chemistry surface grafting was performed by specific hydroxyl chain-ends activation and resulted in bioactive molecules fixation of 20-300pmol/cm2. The photochemical grafting was performed using a molecular clip providing an aromatic azide, for nitrene insertion into a polymer, and an activated ester for grafting of tag compounds. This grafting technique resulted in a dramatic increase in fixed bioactive signals (up to nmol/cm2). The material blood-compatibilization induced by the surface fixation of the inhibitors, was measured by a static blood clot weight measurement test. The wet chemistry grafting technique resulted in moderate blood-compatibilization while by the photochemical grafting method important decrease in surface blood clot formation was observed. In the latter case, the blood response to material contact was found to be strongly affected by the polyester surface photo-degradation induced by the activation treatment.
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Thrombin inhibitors grafting on polyester membranes for the preparation of blood-compatible materialsSalvagnini, Claudio 28 November 2005 (has links)
The design of biomaterials, historically initiated and developed by physicians and engineers, in the last decades has slowly shifted toward a more biochemical based approach. For the replacement, repair and regeneration of tissues scientists are now focusing on materials that stimulate specific biological response at the molecular level. These biomaterials have already shown interesting applications in cell proliferation, differentiation, and extracellular matrix production and organization when the material modifications are designed to elicit specific interactions with cell integrins. In the present work we propose the application of this strategy for the development of blood-compatible materials. We first identified, in the coagulation cascade a key enzyme that constitute a valuable biological target for the development of anti-thrombogenic compounds. Piperazinyl-amide derivatives of N-alfa-(3-trifluoromethyl-benzenesulfonyl)-L-arginine were synthesized as graftable thrombin inhibitors. These inhibitors provided a spacer arm for surface grafting and a fluorine tag for XPS (X-ray photoelectron spectroscopy) detection. The possible disturbance of biological activity due to a variable spacer-arm fixed on the N-4 piperazinyl position was evaluated in vitro against human alfa-thrombin, in silico by molecular modelling and via X-ray diffraction study. Selected inhibitors, having inhibition potency in the mM range, were grafted on polyesters surface via wet chemistry and photochemical activation treatments. Wet chemistry surface grafting was performed by specific hydroxyl chain-ends activation and resulted in bioactive molecules fixation of 20-300pmol/cm2. The photochemical grafting was performed using a molecular clip providing an aromatic azide, for nitrene insertion into a polymer, and an activated ester for grafting of tag compounds. This grafting technique resulted in a dramatic increase in fixed bioactive signals (up to nmol/cm2). The material blood-compatibilization induced by the surface fixation of the inhibitors, was measured by a static blood clot weight measurement test. The wet chemistry grafting technique resulted in moderate blood-compatibilization while by the photochemical grafting method important decrease in surface blood clot formation was observed. In the latter case, the blood response to material contact was found to be strongly affected by the polyester surface photo-degradation induced by the activation treatment.
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Core Level Spectroscopy of Water and IceNordlund, Dennis January 2004 (has links)
A core level spectroscopy study of ice and water is presented in this thesis. Combining a number of experiments and spectrum calculations based on density functional theory, changes in the local valence electronic structure are shown to be sensitive to the local H-bonding configurations. Exploiting this sensitivity, we are able to approach important scientific problems for a number of aggregation states; liquid water, the water-metal interface, bulk and surface of hexagonal ice. For the H-bonded model system hexagonal ice, we have probed the occupied valence electronic structure by x-ray emission and x-ray photoelectron spectroscopy. Stepwise inclusion of different types of interactions within density functional theory, together with a local valence electron population analysis, show that it is essential to include intermolecular charge transfer together with internal s-p rehybridizations in order to describe the changes in electronic structure seen in the experiment. The attractive electrostatic interaction between water molecules is enhanced by a decrease in Pauli repulsion. A simple electrostatic model due to charge induction from the surrounding water is unable to explain the electronic structure changes. By varying the probing depth in x-ray absorption the structure of the bulk, subsurface and surface regions is probed in a thin ice film. A pronounced continuum for fully coordinated species in the bulk is in sharp contrast to the spectrum associated with a broken symmetry at the surface. In particular molecular arrangements of water with one uncoordinated OH group have unoccupied electronic states below the conduction band that are responsible for a strong anisotropic pre-edge intensity in the x-ray absorption spectrum. The topmost layer is dominated by an almost isotropic distribution of these species, which is inconsistent with an unrelaxed surface structure. For liquid water the x-ray absorption spectrum resembles that of the ice surface, indicating a domination of species with broken hydrogen bond configurations. The sensitivity to the local hydrogen bond configuration, in particular the sensitivity to broken bonds on the donor side, allows for a detailed analysis of the liquid water spectrum. Most molecules in liquid water are found in two-hydrogen-bonded configurations with one strong donor and one strong acceptor hydrogen bond. The results, consistent with diffraction data, imply that most molecules are arranged in strongly H-bonded chains or rings embedded in a disordered cluster network. Molecular dynamics simulations are unable to describe the experimental data. The water overlayer on the close-packed platinum surface is studied using a combination of core-level spectroscopy and density functional theory. A new structure for water adsorption on close-packed transition metal surfaces is found, where a weakly corrugated non-dissociated overlayer interacts via alternating oxygen-metal and hydrogen-metal bonds. The latter results from a balance between metal-hydrogen bond formation and OH bond weakening. The ultrashort core-hole lifetime of oxygen provides a powerful probe of excited state dynamics via studies of the non-radiative or radiative decay following x-ray absorption. Electrons excited into the pre-edge state for single donor species at the ice surface remain localized long enough for early time solvation dynamics to occur and these species are suggested as strong pre-existing traps to the hydrated electron. Fully coordinated molecules in the bulk contribute to a strong conduction band with electron transfer times below 0.5 femtoseconds. Upon core-ionization, both protons are found to migrate substantial distances on a femtosecond timescale. This unusually fast proton dynamics for non-resonant excitation is captured both by theory and experiment with a measurable isotope effect.
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Wettability of Methacrylate Copolymer Films Deposited on Anodically Oxidized and Roughened Aluminium SurfacesFrenzel, Ralf, Blank, Christa, Grundke, Karina, Hein, Veneta, Schmidt, Bernd, Simon, Frank, Thieme, Michael, Worch, Hartmut 18 March 2013 (has links) (PDF)
The wetting behavior of water on methacrylate copolymer films was studied on anodically oxidized and micro-roughened aluminium surfaces and also on smooth model surfaces. The copolymerization of tert-butyl methacrylate with a methacrylate containing a fluoroorganic side chain led to a considerable decrease of the surface free energy, but not to a superhydrophobic behavior of polymer-coated, micro-roughened aluminium surfaces. However, copolymers containing both hydrophobic and hydrophilic sequences are able to form superhydrophobic films. X-ray photoelectron spectroscopy showed that an enrichment of the interface between the solid phase and the air by fluorine-containing polymer components was the reason for the strong decrease of the surface free energy. The hydrophilic segments of the copolymers improved the ability to wet the highly polar aluminium surface and to form films of higher density.
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Development Of High Performance Uncooled Infrared Detector MaterialsKebapci, Basak 01 February 2011 (has links) (PDF)
This thesis reports both the optimizations of the vanadium oxide (VOx) thin film as an active infrared detector material by the magnetron sputtering deposition method and its use during fabrication of proper resistors for the microbolometers. Vanadium oxide is a preferred material for microbolometers, as it provides high TCR value, low noise, and reasonable resistance, and a number of high-tech companies have used this material to obtain state-of-the-art microbolometer arrays. This material is first used in microbolometers by Honeywell, who provides its recipe with license agreements, and there is not much information in the literature for its deposition recipe. This is the first study at METU for development of vanadium oxide thin film for microbolometers.
The VOx material deposition studies started by identifying the deposition parameters of the magnetron sputtering system in order to obtain proper VOx resistors for the readout electronics. The obtained recipe includes high temperature deposition
conditions of VOx, however, this causes a diffusion problem on the electrodes, preventing to obtain a good contact to VOx. Also, high oxygen level in the depositions makes a contamination on the electrodes. A number of studies were done to determine a proper electrode material which is proper with the deposition conditions of the VOx.
Characterization of the vanadium oxide samples is done by XRD and XPS measurements to see the relation between the phases and resistivity of the vanadium oxide. It is known that V2O5 phase provides a high TCR and resistivity value, and the XRD results show that this phase is dominant in the highly-oxygen doped or annealed resistors. The TCR and noise measurements are done using resistors implemented with the developed VOx film, after the etching processes of the both VOx and the electrodes are optimized. The contamination on the electrodes is prevented by the help of a newly designed process. The TCR measurement results show that annealing of the resistors affect the TCR values, i.e., increasing the annealing duration increases the TCR values of the resistors. Two different resistors with different deposition conditions are annealed to see the effect of annealing, where TCR results of the resistors are -0.74%/K and -0.8 %/K before annealing. The TCR values of these resistors increase to -1.6 %/K and -4.35 %K, respectively, after annealing in same conditions, showing that both the deposition conditions and annealing change the TCR significantly. Although good TCR values are obtained, the noise values of the VOx resistors are much higher than the expected values, which suggest a further study to determine the cause of this noise.
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