An uniform titanium oxide film was grown on indium tin oxide/glass substrate with the aqueous solutions of ammonium hexafluoro-titanate and boric acid. The as-deposition titanium oxide film shows good electrochromic property because of fluorine passivation on defects and dangling bonds. The transmittance of as-grown titanium oxide on indium tin oxide/glass with a thickness of 270 nm is about 85% at the wavelength of 550 nm. By 50 times electrochromic cycling test, the transparency ratio of TiO2 film is kept at 45% between fully colored state and fully bleached state at the wavelength of 550 nm. Under ultraviolet illumination, the growth of titanium oxide film grown is enhanced. The root mean squared value of surface roughness is improved from 3.723 to 0.523 nm. Higher fluorine concentration from (NH4)2TiF6 passivate defects and dangling bonds of titanium oxide during the growth. After 50 times electrochromic cycling test, the transparency ratio UV-TiO2 is improved from 37.5% to 42.4% at the wavelength of 550 nm. The electrical characteristics of nickel-doped titanium oxide films on p-type (100) silicon substrate by liquid phase deposition were investigated. For nickel doping, the nickel chloride was used as the doping solution and the electrical characteristics were improved. After thermal annealing in nitrous oxide at 700 oC, the dielectric constant of polycrystalline titanium oxide film is 29 and can be improved to 94 with nickel doping. Uniform nickel oxide film was grown on a conducting glass substrate with the aqueous solution of saturated NiF2¡E4H2O solution and H3BO3. The quality of NiO is improved after thermal annealing at 300 oC in air from the decrease of oxygen vacancy and better F ion passivation on defects and dangling bonds. The transmittance of as-deposited NiO/ITO/glass with a thickness of 100 nm is about 78% and improved to 88% after annealing at the wavelength of 550 nm. By the electrochromic cycling test 50 times on annealed NiO film, the transparency ratio is kept at 48% between fully colored state and fully bleached state at the wavelength of 550 nm. By the memory time test, the annealed LPD-NiO film has shorter memory time. The growth of nickel oxide film grown on indium-tin oxide/glass substrate by liquid phase deposition is enhanced under ultraviolet photo-irradiation was studied. a-Ni(OH)2 dominates the composition of as-grown NiO film. After thermal treatment at 300 oC,a-Ni(OH)2 is transformed into NiO. For thermally treated NiO under ultraviolet photo-irradiation, the recrystallization and the colored and bleached transmittance after 50 times electrochromic test were improved. Both improvements come from fluorine passivation. Transparent and conductive thin films consisting of p-type nickel oxide (NiO) semiconductors were prepared by liquid phase deposition. A resistivity of 8 x 10-1 -cm was obtained for NiO films prepared at liquid phase deposition. The transmittance of NiO is almost 70 % in the 550 nm wavelength was obtained for a 384.3 nm thick NiO film.

In this study, the characteristics of LPD-NiO, and lithium-doped LPD-NiO filmson glass substrate were investigated. In our experiment, we do some measurement about physical, chemical, electrical and optical properties for LPD-NiO and lithium-doped LPD-NiO films and discussed with them. The NiO film thickness was characterized by field emission scanning electron microscopy (FE-SEM), structure was characterized by X-ray diffraction (XRD), chemical properties were characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). Electrical properties were characterized by four-point probe, and optical properties were characterized by a reflecting spectrograph. The thermal annealing was used to improve the characteristics of LPD-NiO and lithium-doped LPD-NiO films in nitrogen, air and nitrous oxide ambient. For lithium doping, the lithium chloride was used as the doping solution and the electrical characteristics were enhanced. After thermal annealing in air at 400 oC, the resistivity of NiO films is 7.5 ¡Ñ 10-1 ohm-cm and can be lowed to 7.2 ¡Ñ 10-3 ohm-cm with lithium doping.

This thesis investigates the electrochromic NixW1-x oxide thin film system, where 0 < x < 1. The thin films were deposited by reactive DC magnetron co-sputtering from one Ni and one W metal target. In addition, Ni oxide was deposited with water vapor added to the sputtering gas. The different compositions were structurally characterized by X-ray diffraction, X-ray photoelectron-, Rutherford backscattering- and Raman spectroscopy. Possible nanostructures were studied by ellipsometry together with effective medium theory. Optical and electrochemical properties were investigated by spectrophotometry and cyclic voltammetry in 1 M lithium perchlorate in propylene carbonate (Li-PC). Li-PC electrolyte was used as it is being compatible with both W and Ni oxides. Few studies have previously been made on Ni oxides in Li-PC. Films with high Ni content, 0.85 < x < 1, were polycrystalline and all other films were amorphous. W-rich films, x < 0.5, consisted of a mixture of W oxide and NiWO4 -phases, and the Ni-rich samples, x > 0.5, probably consisted of hydrated Ni oxide and NiWO4 -phases. Films with 0 < x < 0.3 showed electrochromic properties similar to W oxide, and films with 0.7 < x < 1 behaved as Ni oxide. For 0.4 < x < 0.7 no optical change was seen. At the border of cathodic electrochromic and non-electrochromic behavior, i.e. x ~ 0.4, the sample behaved as an optically passive intercalation material. The transmittance change was 0.45 and 0.15 for the W-rich and Ni-rich films, respectively. Ni addition to W oxide improved the coloration efficiency. For the Ni-rich films the charge insertion/extraction and optical modulation was low and an aging effect resulted in strong bleaching of the samples. The advantage of W addition to Ni oxide was that the transparency at the bleached state was enhanced. Moreover, it was found that the hydrous character of the Ni oxide had a large impact on the electrochromic performance, both when electrochemically cycled in KOH and in the non-aqueous Li-PC.

L’électrochromisme se définit par la capacité d’un système à modifier ses propriétés optiques en réponse à une tension électrique. Aujourd’hui, les vitrages intelligents sont une des applications phare. Ce manuscrit contribue à une meilleure compréhension du mécanisme responsable de la commutation optique du matériau à coloration anodique NiO. Des films de stoechiométrie contrôlée, de formule Ni1-xO, ont été déposés par pulvérisation cathodique à température ambiante sous différentes pressions partielles d’oxygène. De nature faiblement cristallisés, la caractérisation des films par diverses techniques telles que la spectroscopie de photoélectrons X, ou la spectroscopie de pertes d’énergie des électrons a permis d’estimer que la stoechiométrie variait de Ni0,96O à Ni0,81O lorsque la P(O2) augmentait de 2% à 10%. L’étude électrochimique couplée aux mesures optiques, du film Ni0,96O dans divers électrolytes lithié et non-lithié, a montré que la différence de couleur entre l’état décoloré et coloré (marron) était comparable (42%<ΔT=Tdec-Tcol<55%) quel que soit le milieu. Ces résultats ont conduit à la mise en évidence d’un mécanisme régi simultanément par un comportement faradique et capacitif. L’intégration des films dans des dispositifs Ni1-xO/WO3 est associée à une coloration neutre quelles que soient les épaisseurs des couches unitaires ou la température de cyclage. Toutefois, des températures de cyclage supérieures à 45°C ont conduit à des dégradations irréversibles des propriétés électrochromes tandis que des températures de cyclage négatives ont entrainé une diminution voire une disparition des propriétés électrochromes. La conception de dispositifs plus originaux, double face, conclut ce manuscrit. / Electrochromism is defined by the ability of a system to modify its optical properties in response to an electrical voltage and today, its flagship application is the smart windows. This manuscript contributes to a better understanding of the mechanism responsible of the coloration of the anodically colored oxide NiO. Non-stoichiometric films, Ni1-xO, were deposited by sputtering at room temperature under different partial pressures of oxygen. The characterization of the films by various techniques, including X-ray photoelectron spectroscopy or energy loss spectroscopy, has led to the conclusion that the stoichiometry varied from Ni0.96O to Ni0,81O when P(O2) increased from 2% to 10%. The electrochemical study coupled with the optical measurements of Ni0,96O film in various lithiated and non-lithiated electrolytes showed that the color difference between the bleached and colored (brownish) state was comparable (42%<ΔT=Tbl-Tcol<55%) regardless of the electrolyte nature. These results led to the identification of a mechanism simultaneously governed by a faradaic and capacitive behavior. The integration of the films in Ni1-xO/WO3 devices is associated to neutral colored ECDs regardless of the thickness of the individual layers or the cycling temperature. However, cycling temperatures above 45°C has led to irreversible degradations of the electrochromic properties while negative cycling temperatures has shown a decrease or even disappearance of the electrochromic properties. The design of original devices concludes this manuscript.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, nickel oxide films were prepared from the Spray Pyrolysis Technique, due to its wide application in the manufacture of various electronic devices and intense study of its semiconducting properties. The films were obtained from a precursor solution containing 0.2 mol / L NiCl2 dissolved in distilled water containing sucrose as a chelating agent, deposited on a glass substrate temperature of 450 ° C. The sucrose concentration in the solution ranged from 0 to 10 × 10-3 mol/L and its effects on structural, morphological and optical properties were studied using the techniques of X-ray diffraction, scanning electron microscopy and UV-vis spectroscopy. It was observed that, before the concentration of sucrose, the films have different optical characteristics (transparent or opaque) for amorphous or crystalline films. / Neste trabalho, foram preparados filmes de óxido de níquel, a partir da Técnica Spray Pirólise, devido à sua grande aplicação na fabricação de diversos dispositivos eletrônicos e intenso estudo de suas propriedades semicondutoras. Os filmes foram obtidos a partir de uma solução precursora contendo 0,2 mol/L de NiCl2 dissolvido em água destilada, contendo a sacarose como agente quelante, depositados sobre um substrato de vidro a temperatura de 450°C. A concentração de sacarose na solução variou de 0 a 10×10-3 mol/L e seus efeitos nas propriedades estruturais, morfológicas e ópticas foram estudadas através das técnicas de Difração de Raios X, Microscopia Eletrônica de Varredura e Espectroscopia UV-vis. Observou-se que, diante da concentração de sacarose, os filmes apresentam diferentes características ópticas (transparentes ou opacos) para filmes amorfos ou cristalinos.

No presente trabalho foram preparados eletrodos formados por filmes finos de níquel e óxido de níquel sobre um substrato de Ti. Estes eletrodos foram preparados pelas metodologias de decomposição térmica de precursores poliméricos; método sol-gel e eletrodeposição com a finalidade de investigar a influência da metodologia de preparação sobre sua atividade catalítica. Foram avaliadas as variáveis relacionadas ao processo de preparação dos eletrodos como, por exemplo, a temperatura e a atmosfera de calcinação, além de diferentes métodos de eletrodeposição. A caracterização dos eletrodos foi realizada por técnicas de difração de raios-x; microscopia eletrônica de varredura e voltametria cíclica. Os resultados obtidos indicaram que as metodologias utilizadas proporcionaram a preparação de eletrodos com alta área superficial devido à formação de morfologias contendo trincas, fissuras e microrrachaduras. Por meio destas análises foi possível obter um quadro amplo do comportamento destes eletrodos. Os eletrodos preparados pelas três metodologias foram utilizados no estudo da eletrooxidação do furfural, que foi realizado através de cronopotenciometria. Os produtos foram analisados por CLAE (Cromatografia Líquida de Alta Eficiência) com intuito de analisar a eficiência dos eletrodos na eletrooxidação. Os resultados obtidos foram satisfatórios sendo que os eletrodos preparados pela metodologia de sol-gel apresentaram um maior rendimento na formação de ácido furóico. / In the present work we prepared electrodes formed by thin nickel and nickel oxide films on a Titanium substrate. These electrodes were prepared by thermal decomposition of polymeric precursors, sol-gel method and electroplating arming at investigate the influence of the preparation methodology on their catalytic activity. The parameters related to the electrodes preparation process had been investigated. These parameters included temperature and atmosphere calcinations, beyond different methods of electroplating. The electrodes characterization were carried out by x-ray diffraction, scanning electronic microscopy and cyclic voltammetry. The results indicate that the used methodologies provided the preparation of electrodes with high superficial area due to the formation of cracked and porous morphologies. he electrodes prepared by the different methodologies were used in the furfural eletrooxidation study, which was carried out by chronopotentiometry. The products were analyzed by HPLC (High Performance Liquid Chromatography) to verify the electrodes efficiency in the eletrooxidation. The obtained results had been satisfactory and the electrodes prepared by sol-gel method present a higher efficiency for furoic acid formation.

L'objectif de cette thèse est l'obtention de nouvelles données expérimentales en milieu acide borique dans le cadre du développement de modèles décrivant le comportement des produits de corrosion dans le circuit primaire, et notamment sur le relâchement du nickel par des phénomènes de dissolution/précipitation. Le travail présenté dans ce mémoire s'est focalisé sur une des phases solides du nickel, l'oxyde de nickel (NiO), ainsi que sur le comportement en solution de sa forme ionique, Ni2+. La solubilité de l'oxyde de nickel a été mesurée à haute température à l'aide d'un réacteur à circulation ouverte spécialement conçu pour fonctionner à haute température et haute pression. Compte tenu des concentrations très faibles en Ni dans les conditions de nos essais (300°C, pH>7, matrice bore-lithium), une méthode d'analyse du nickel dissous à l'échelle de l'ultra-trace (ng.kg-1) en milieu bore-lithium a été développée par ICP-MS et a été validée statistiquement par la méthode du profil d'exactitude. La complexation du nickel par les (poly)borates a ensuite été étudiée. Une expérience a été conduite où les ions nickel sont progressivement formés par oxydation d'une électrode de nickel métallique dans une solution d'acide borique. Basé sur les résultats expérimentaux et sur la modélisation de la spéciation aqueuse du bore, l'évolution du pH a montré l'existence significative d'un complexe nickel-bore. Le complexe neutre NiB3O4(OH)3 a été mis en évidence pour de fortes concentrations en acide borique, lorsque les polyborates sont présents. Les constantes d'équilibres ont été calculées à 25, 50 et 70°C, ainsi que les données thermodynamiques associées. Enfin, les cinétiques de dissolution de l'oxyde de nickel ont été mesurées en milieu acide chlorhydrique et en milieu acide borique de 25 à 100°C et un pH de 6. Les résultats ont mis en évidence un effet inhibiteur de l'acide borique sur les vitesses de dissolution de NiO dont le phénomène est exacerbé par l'augmentation de la température et de la concentration en bore. La formation d'un complexe surfacique a été mise en avant pour expliquer cet effet. / This work focuses on the nickel oxide phase (NiO) and the behavior in solution of its ionic form Ni2+. The solubility of nickel oxide has been determined at high temperature and pressure by the use of a flow through cell reactor specially designed to perform measurements in the conditions of the primary circuit. Because the solubility of nickel is very low at 300°C and pH>7, a new method for the determination of ultra-traces nickel concentrations in lithium/boron medium by ICP-MS coupled with a desolvator system nebulizer has been developed and validated by the statistical approach of accuracy profiles. The complexation of nickel by the (poly)borates has been also studied. Based on the experimental results and aqueous speciation modeling, the evolution of pH showed the existence of significant nickel-boron complexation. A neutral complex NiB3O4(OH)3 was postulated at high boric acid concentrations when polyborates are present, and the equilibrium constants were determined at 25, 50 and 70°C. The associated thermodynamics data have also been determined. Dissolution rates of nickel oxide have been measured in hydrochloric acid and in boric acid media up to 100°C and pH 6. Results showed that boric acid inhibits the dissolution rates of NiO and this phenomenon is enhanced by the temperature and the concentration of boron. The formation of a surface complex was postulated to explain this effect.

P-type transparent conductors are needed for a wide range of applicationssuch as solar cells and electrochromic smart windows. Solar power is animportant form of energy in today’s society as the threat of global warmingpushes the world towards fossil free energy. Hence a lot of solar cell typeshave been developed, among them tandem cells which are to different typesof solar cells stacked on top of each other. If one of the cells is based ona perovskite, a transparent p-type thin film electrode is needed as a holeconductor and electron blocking layer between the two cells. Nickel oxide(NiO) is a good candidate for this application as it has desired propertiessuch as good hole conduction, a high band gap and a matching work functionto the perovskite. The transmittance of as deposited NiO films by reactivemagnetron sputtered is limited so post deposition annealing is used to increasethe transmittance. This is not possible in this solar cell application as parts ofthe solar cell stack is temperature sensitive.Electrochromic smart windows contain a layer that can change its opticalproperties with the application of a voltage. Such windows are used inbuildings to increase energy efficiency and they contain an electrochromicdevice where NiO is used as an electrode as it has electrochromic properties,but just like with the solar cells, the transmittance of NiO is limited. Thisstudy investigates whether it is possible to make as deposited NiO by reactivemagnetron sputtering transparent, eliminating the need for post depositionannealing. Such a deposition process was found using different sputtermachines with the process point on the edge between metal and oxide modein terms of oxygen flow. This resulted in highly transparent and highlyresistive NiO films with a much higher deposition rate than in oxide mode.

[ES] La presente tesis doctoral se sitúa en el marco de la actual transición energética, que plantea la sustitución progresiva de materias primas de origen fósil por fuentes renovables, tanto para la obtención de productos químicos como para la producción de combustibles. En este contexto de transición paulatina a las renovables, y teniendo en cuenta los últimos pronósticos, las fuentes fósiles (fundamentalmente gas natural) y derivados de la biomasa, jugarán un papel fundamental durante el cambio. Se ha llevado a cabo un estudio sobre el empleo de óxidos metálicos (basados en bronces de wolframio o en óxido de níquel), como catalizadores para: i) la transformación de derivados de biomasa: de glicerol a acroleína/ácido acrílico; y de compuestos oxigenados de cadena corta presentes en efluentes acuosos (procedentes de tratamientos de extracción de bio-aceites de pirolisis) a combustibles; y ii) la transformación de componentes del gas natural, concretamente la obtención de etileno a partir de etano, mediante deshidrogenación oxidativa (ODH). El trabajo se presenta desde una perspectiva de la química de materiales, haciendo hincapié en las propiedades fisicoquímicas de los distintos sistemas catalíticos, empleando técnicas de caracterización convencionales e in situ, además de reacciones modelo (transformación de metanol y etanol), con el objetivo de entender las funciones catalíticas presentes en cada caso. Tanto para la transformación de glicerol en fase gas, como para la valorización de mezclas acuosas de compuestos oxigenados de cadena corta, se han utilizado catalizadores basados en bronces de wolframio. Se ha tratado de poner de manifiesto la gran versatilidad composicional y estructural (con el consiguiente control de las propiedades funcionales), que presentan este tipo de materiales. En este sentido, las propiedades ácidas y redox de catalizadores W-V-O pueden ser moduladas, para una misma concentración de vanadio, mediante el control de la relación de fases cristalinas (hexagonal y monoclínica) del óxido de wolframio. Este efecto se ha estudiado empleando la transformación aeróbica de metanol como reacción "test", y tiene una gran influencia en la deshidratación oxidativa de glicerol a ácido acrílico. A su vez, mediante la sustitución isomórfica de wolframio por niobio (en el sistema WO3-Nb2O5) es posible controlar la relación de centros ácidos de tipo Brönsted y Lewis en la superficie de los materiales. Por un lado, los catalizadores con una alta relación Brönsted/Lewis se han mostrado más efectivos en la deshidratación de glicerol a acroleína, mientras que los catalizadores con altas concentraciones de centros de tipo Lewis presentan altos rendimientos a productos de condensación de compuestos oxigenados de cadena corta. Adicionalmente se han estudiado las diferencias entre catalizadores (bien óxidos mixtos W-V-O o W-Nb-O) preparados mediante un método hidrotermal o mediante reflujo, así como el efecto de la utilización de un soporte mesoporoso (KIT-6), sobre sus propiedades catalíticas en la transformación aeróbica en fase gaseosa de etanol y glicerol. Finalmente, en lo que concierne a la transformación de componentes del gas natural, se han empleado materiales basados en óxido de níquel (soportado sobre distintos óxidos y/o promovido con distintos metales) como catalizadores para la ODH de etano. En este caso el estudio se ha centrado fundamentalmente en dilucidar los efectos de promotores y soportes en la naturaleza y propiedades fisicoquímicas del óxido de níquel, los cuales dan lugar a un cambio drástico en sus propiedades catalíticas. Así, se ha observado que modificando la reducibilidad y las características superficiales del óxido de níquel es posible transformar un catalizador muy poco selectivo en la ODH de etano (como es el NiO, con una selectividad a etileno del 30 %) en uno de los catalizadores más selectivos para llevar a cab / [CA] Aquesta tesi doctoral es situa dins del marc de l'actual transició energètica, la qual planteja la substitució progressiva de les primeres matèries d'origen fòssil per fonts renovables, tant per a l'obtenció de productes químics com per a la producció de combustibles. En aquest context de transició gradual a les renovables, i tenint en compte els últims pronòstics, les fonts fòssils (principalment el gas natural) i els derivats de la biomassa, exerciran un paper fonamental durant aquest canvi. S'ha dut a terme un estudi sobre la utilització d'òxids metàl·lics (basats en bronzes de wolframi o en òxid de níquel), com a catalitzadors per a: i) la transformació de derivats de la biomassa: de glicerol a acroleïna/àcid acrílic; i de compostos oxigenats de cadena curta presents en efluents aquosos (procedents de tractaments d'extracció de bio-olis de la piròlisi) a combustibles; i ii) la transformació de components del gas natural, concretament l'obtenció d'etilè a partir d'età, mitjançant la deshidrogenació oxidativa. El treball es presenta des del punt de vista de la química de materials, posant l'accent en les propietats fisicoquímiques dels diferents sistemes catalítics, utilitzant tècniques de caracterització convencionals i in situ, a més de reaccions model, amb l'objectiu d'entendre les funcions catalítiques presents en cadascun dels casos. Tant per a la transformació del glicerol en fase gasosa com per a la valorització de les mescles aquoses de compostos oxigenats de cadena curta, s'han utilitzat catalitzadors basats en bronze de wolframi. S'ha intentat posar de manifest la gran versatilitat de composicions i estructures (amb el conseqüent control de les propietats funcionals) que presenten aquest tipus de materials. En aquest sentit, les propietats àcides i redox dels catalitzadors de W - V - O poden ser modulades, per a una mateixa concentració de vanadi, mitjançant el control de la relació de fases cristal·lines (hexagonal i monoclínica) de l'òxid de wolframi. Aquest efecte s'ha estudiat utilitzant la transformació aeròbica de metanol com a reacció "test", i presenta una gran influència en la deshidratació oxidativa de glicerol a àcid acrílic. Al mateix temps, mitjançant la substitució isomòrfica de wolframi per niobi (en el sistema WO3 - Nb2O5), és possible controlar la relació de centres àcids de tipus Brönsted i Lewis en la superfície dels materials. Per una part, els catalitzadors que presenten una relació Brönsted / Lewis alta s'han mostrat més efectius en la deshidratació de glicerol a acroleïna, mentre que els catalitzadors amb unes altes concentracions de tipus Lewis presenten alts rendiments a productes de condensació de compostos oxigenats de cadena curta. Addicionalment, s'han estudiat les diferències entre catalitzadors (ja siguin òxids mixtos W-V-O o W-Nb-O) preparats mitjançant un mètode hidrotermal o mitjançant un mètode de reflux, així com l'efecte que presenta la utilització d'un suport mesoporós (KIT-6), sobre les seves propietats catalítiques en la reacció de transformació aeròbica en fase gasosa d'etanol i glicerol. Finalment, pel que fa referència a la transformació de components del gas natural, s'han utilitzat materials basats en òxid de níquel (suportat sobre diferents òxids i/o promoguts amb diferents metalls) i catalitzadors per a la deshidrogenació oxidativa d'età. En aquest cas, l'estudi s'ha focalitzat principalment en dilucidar els efectes de promotors i suports en la naturalesa i propietats fisicoquímiques de l'òxid de níquel, els quals impliquen un canvi dràstic en les seves propietats catalítiques. Així doncs, s'ha observat que modificant la reductibilitat i les característiques superficials de l'òxid de níquel és possible transformar un catalitzador molt poc selectiu en la deshidrogenació oxidativa de l'età (com és el cas del NiO, amb una selectivitat a l'etilè del 30%) en un dels cata / [EN] The present doctoral thesis is set within the scope of the current energy transition, which considers the progressive substitution of non-renewable fossil sources by renewable feedstocks for the production of chemicals and fuels. In this context of gradual transition, and according to recent energy outlooks, fossil sources (especially natural gas) and biomass feedstocks will play a key role during the shift. A study on the use of metal oxides (based on tungsten bronzes or nickel oxides) as catalysts for different reactions has been conducted. Particularly, they have been studied as catalytic materials for: i) the transformation of biomass-derived feedstocks: glycerol transformation into acrolein/acrylic acid, and the transformation of short-chain oxygenates present in aqueous effluents (derived from extraction processes of pyrolysis bio-oils) into fuels; and ii) the valorization of natural gas components, i.e. the transformation of ethane into ethylene by oxidative dehydrogenation. The work is presented from a materials chemistry perspective, emphasizing the physicochemical characteristics of the different catalytic systems by using conventional and in situ characterization techniques and model reactions (gas phase methanol and ethanol transformation); with the aim of understanding the specific catalytic functionalities present in each case. For both gas phase glycerol transformation and the valorization of short-chain oxygenates aqueous mixtures, catalyst based on tungsten oxide bronzes have been used. The compositional and structural versatility of this structural types (with the subsequent control of their functional properties) will be highlighted. In this sense, the acid-redox properties of W-V-O catalysts can be modulated by controlling the crystalline phase composition in the materials (i.e. hexagonal and monoclinic polymorphs of tungsten oxide) at a fixed V concentration. This effect has been studied by using the gas-phase aerobic transformation of methanol as a surface test reaction. The concentration of the hexagonal and monoclinic polymorphs in the catalysts has also an important influence in the gas-phase transformation of glycerol into acrylic acid. Also, it is possible to control the Brönsted/Lewis acid nature of the surface by the isomorphic substitution of Nb for W in WO3-Nb2O5 system. On the one hand, catalysts showing a higher proportion of Brönsted acid sites are more effective in the glycerol dehydration to acrolein. On the other hand, materials with a higher concentration of Lewis acid sites display high yields to condensation products in the aqueous phase valorization of short chain oxygenates. Additionally, the differences between W-V-O and W-Nb-O catalysts prepared by both reflux and hydrothermal methods have been studied. Also the effect of adding a mesoporous KIT-6 silica as support on the catalytic performance in the gas phase transformation of ethanol and glycerol will be underlined. Considering the transformation of natural gas components, nickel oxide-based materials were chosen (either supported on different oxides and/or promoted with different metals) to perform the oxidative dehydrogenation (ODH) of ethane. In this case the study has been focused on elucidating the effects of both promoters and supports on the nature and physicochemical features of nickel oxide, which lead to a drastic change in the catalytic behavior of these materials. This way, it has been observed that by the modification of the reducibility and the chemical nature of nickel oxide, it is possible to transform an apparently non-selective catalyst in the ODH of ethane (like NiO, showing a selectivity to ethylene of ca. 30 %) into one of the most selective catalysts reported in the literature (presenting a selectivity to ethylene of ca. 90 %). / También me gustaría agradecerle al Prof. Avelino Corma, investigador principal del proyecto SEV-2012-0267, a través del cual he podido realizar mi tesis doctoral enel Instituto de Tecnología Química (SVP-2014-068669). / Delgado Muñoz, D. (2019). Catalytic valorization of natural gas and biomass-derived feedstocks by metal oxides [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/122298 / TESIS

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18285号 / 工博第3877号 / 新制||工||1595(附属図書館) / 31143 / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 木本 恒暢, 教授 藤田 静雄, 准教授 掛谷 一弘 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM