L'éthanol est converti, à 350°C sous 30 bar et sur des zéolithes protoniques, en un mélange de paraffines légères et d'aromatiques ; produits incorporables dans le pool essence. Cependant, la transformation de EtOH sur zéolithes acides conduit à la formation du coke. Des techniques physiques avancées, en particulier les techniques MALDI et LDI-TOF MS, couplées à la méthode d'analyse qui consiste à récupérer dans un solvant les molécules carbonées après dissolution de la zéolithe dans HF, contribuent à caractériser finement le coke. Sa composition dépend du catalyseur : sur HBEA(11), zéolithe à larges pores, 17 familles ont été détectées contre 4 sur HZSM-5(40) de taille de pore intermédiaire. Sur cette dernière, le coke, composé de polyalkybenzènes / naphtalènes / phénalènes et pyrènes, est localisé à l'intersection des canaux et a une toxicité vis-à-vis des sites acides de Brønsted de 1. En dépit d'un empoisonnement total, cette zéolithe est toujours capable de convertir EtOH, comme MeOH, en hydrocarbures et qui plus est avec les mêmes sélectivités en produits. La transformation de ces deux alcools ne s'explique pas par un mécanisme classique de catalyse acide, mais par un mécanisme concerté radicalaire-acide. La présence d'un inhibiteur de radicaux dans la charge réactionnelle, l'hydroquinone, provoque une désactivation immédiate et une diminution de la concentration des radicaux. La transformation de EtOH et MeOH passe par un intermédiaire réactionnel commun, le carbène :CH2, dont l'oligomérisation radicalaire conduit à la formation d'oléfines. Ces oléfines légères (n-O3-n-O5) sont très réactives et se transforment par catalyse acide (oligomérisation / cyclisation / t / Ethanol is converted into light paraffins and aromatics mixture at 350°C under 30 bar over protonic zeolites. These products can be incorporated in the gasoline pool. Nevertheless, EtOH transformation over acid zeolites leads to the formation of the coke. Advanced physical techniques, in particular MALDI and LDI-TOF MS, were coupled to the coke analysis method. This method consists of the recovery of the carbonaceous molecules in a solvent after zeolite dissolution in hydrofluoric acid solution. This coupling allows characterizing the coke through an extensive way. The coke composition depends on the catalyst morphology: over HBEA(11) zeolite of large pores, 17 families were detected while 4 over HZSM-5(40) of intermediate pore size. Over this latter, the coke, composed of polyalkylbenzenes/naphtalenes/phenalenes and pyrenes, is located in the channels intersections and has toxicity of 1 towards Brønsted acid sites. In spite of a total poisoning, HZSM-5 zeolite is always able to convert EtOH, like MeOH, into hydrocarbons with the same products selectivity. The transformation of the two alcohols cannot be explained by a classical mechanism of acid catalysis, but by a cooperative radical-acid mechanism. The presence of a radical inhibitor in the feed, the hydroquinone, causes an immediate deactivation and a decrease in the concentration of radicals. The transformation of EtOH and MeOH passed by the common reaction intermediate, the :CH2 carbene, which its radical oligomerization leads to the formation of olefins. Olefins (n-O3-n-O5) are very active and can be transformed through acid catalysis (oligomerization/cyclisation/Hydrogen transfer) into aromatics or undergo isomer

Le méthanethiol est un intermédiaire clé dans la synthèse de la méthionine, un acide aminé largement utilisé dans l'industrie agro-alimentaire. / Methanethiol is a key intermediate in methionine synthesis, an amino-acid which is widely used in food-processing industry.

DME est un carburant propre qui contribue à diminuer les émissions de gaz à effet de serre; il est aussi une molécule plate-forme pour le stockage d'énergie. L'objectif de la thèse est le développement de matériaux catalytiques bifonctionnels pour la synthèse directe de DME à partir de CO2/H2 à partir de Cu/ZnO/ZrO2 comme le catalyseur de la synthèse de méthanol à partir de CO2/H2 et Al-TUD-1 comme le catalyseur de déshydratation du méthanol en DME. Dans cette thèse, Al-TUD-1 a été étudiée comme un catalyseur de la déshydratation du méthanol en DME pour la première fois. Son activité en déshydratation du méthanol en DME augmente avec la diminution du rapport Si/Al. Les catalyseurs bifonctionnels ont été préparés par un procédé de dépôt par co-précipitation. Le SMSI a été démontré et était bénéfique pour la dispersion de cuivre métallique, la surface de cuivre métallique augmente avec le rapport Si/Al. Dans le même temps, on a observé le blocage des sites acides d'Al-TUD-1 par le cuivre. Afin d'exposer les sites acides d'Al-TUD-1, la méthode de « core-shell » a été adoptée pour préparer le catalyseur bifonctionnel. Elle aide à libérer la fonction acide en empêchant son blocage par le cuivre. Cette méthode de synthèse a été bénéfique pour la stabilité des particules de cuivre métalliques, mais des faibles conversions de CO2/H2 ont été observées en raison de l'inaccessibilité du noyau. Un autre catalyseur bifonctionnel a été préparé par une méthode de mélange physique pour comparaison. L'optimisation du catalyseur bifonctionnel Cu/ZnO/ZrO2@Al-TUD-1 pour la synthèse directe de DME à partir de CO2/H2 a permis d'éclairer les principaux paramètres affectant le contact intime de deux fonctions catalytiques: surface et dispersion du cuivre, les propriétés acide et basic, la présence d'eau et l'accessibilité des sites actifs pour les réactifs. / DME is a clean fuel that helps to diminish the emissions of green house gases; it is as well a platform molecule for the energy storage. The objective of the thesis is the development of bifunctional catalytic materials for the direct DME synthesis from CO2/H2 based on Cu/ZnO/ZrO2 as the methanol synthesis from CO2/H2 catalyst and Al-TUD-1 as the methanol dehydration to DME catalyst. In this thesis, Al-TUD-1 was investigated as the methanol dehydration to DME catalyst for the first time. The methanol dehydration to DME performance increases with the decrease of Si/Al ratio. The bifunctional catalysts were prepared by co-precipitation deposition method. The SMSI was demonstrated and was beneficial for the metallic copper dispersion, the metallic copper surface area increases with the Si/Al ratio. In the same time the blockage of acid sites of Al-TUD-1 by copper was observed. In order to expose the acid sites of Al-TUD-1, the core shell method was adopted to prepare the bifunctional catalyst. It helps to free the acid function preventing its blockage by copper. This method of synthesis was beneficial for the stability of metallic copper particles, but performed low conversions of CO2/H2 due to the inaccessibility of the core. Another bifunctional catalyst was prepared by physically mixing method for comparison. The optimization of the bifunctional Cu/ZnO/ZrO2@Al-TUD-1 catalyst for the direct DME synthesis from CO2/H2 allowed enlightening the main parameters that affect the intimate contact of two catalytic functions: copper surface area and dispersion, acid and basic properties, water presence and the accessibility of the active sites for the reactants.

En situation d’interaction pastille-gaine (IPG), les gaines de crayons combustible en alliage de zirconium sont susceptibles de rompre lors de transitoires de puissance incidentels dans les réacteurs à eau pressurisée, par un mécanisme de corrosion sous contrainte induite par l’iode (CSC-I). Cette étude traite de l’amorçage intergranulaire des fissures de CSC-I dans le Zircaloy-4 recristallisé, en milieu méthanol iodé à température ambiante, en s’intéressant particulièrement aux paramètres mécaniques critiques et à la concentration en iode. Pour cela, une approche mêlant expériences et simulations numériques a été adoptée. Un modèle de comportement mécanique macroscopique de l’alliage, viscoplastique et anisotrope, a été établi et validé sur une large gamme de sollicitations. Par la réalisation de nombreux essais de traction à vitesse de déformation imposée et de fluage en flexion quatre points, nous avons montré l’existence d’une concentration seuil I0 proche de 10-6 g.g-1 nécessaire à l’apparition du dommage de CSC-I, mais également celle d’une concentration de transition I1 proche de 2 10-4 g.g-1 au-delà de laquelle le mécanisme change, menant à un amorçage anticipé des fissures et une sensibilité réduite de l’endommagement aux paramètres mécaniques. L’importance de la concentration sur des paramètres tels que la densité des fissures, leur longueur moyenne et la vitesse de propagation intergranulaire et transgranulaire a été mise en évidence. Les résultats expérimentaux montrent que la déformation plastique macroscopique n’est pas indispensable à l’amorçage de fissures de CSC-I, pour un temps d’essais suffisamment long en présence de contrainte. Son principal effet est de précipiter l’apparition de fissures par la création de sites d’amorçage, par rupture de la couche d’oxyde et accumulation de contrainte intergranulaire. En dessous de I1 la détermination des déformations critiques à l’amorçage montre un fort effet de vitesse. Dans ce domaine, une contrainte seuil de 100 MPa a été déterminée, bien inférieure à la limite élastique. L’utilisation d’éprouvettes entaillées et de la simulation numérique a permis de mettre en évidence un fort effet protecteur de l’augmentation de la biaxialité des contraintes vis-à-vis de l’amorçage, dans le domaine élastique comme dans le domaine plastique. Des éprouvettes préalablement irradiées aux protons à une dose de 2 dpa ont été testées dans les mêmes conditions que les éprouvettes non irradiées. La sensibilité accrue du matériau irradié à la CSC-I a pu être quantifiée et nous avons constaté qu’un effet de concentration et un effet de vitesse de sollicitation subsistent après irradiation. L’irradiation induit une localisation plus importante de la déformation menant à un amorçage prématuré des fissures, mais une sensibilité chimique plus importante, tendance à la piquration et décalage de I1, apparaît comme le principal responsable de la plus forte sensibilité de l’irradié. / During the pellet-cladding interaction, Zirconium-alloy fuel claddings might fail when subjected to incidental power transient in nuclear Pressurized Water Reactors, by Iodine-induced Stress Corrosion Cracking (I-SCC). This study deals with the intergranular initiation of I-SCC cracks in fully recrystallized Zircaloy-4, in methyl alcohol solution of iodine at room temperature, with the focus on critical mechanical parameters and iodine concentration. It was carried out with an approach mixing experiments and numerical simulations. An anisotropic and viscoplastic mechanical behavior model was established and validated over a wide range of loadings. With numerous constant elongation rate tensile tests and four points bending creep tests, the existence of a threshold iodine concentration I0 close to 10-6 g.g-1 was highlighted, necessary to the occurrence of I-SCC damage, along with a transition concentration I1 close to 2 10-4 g.g-1. Above I1 the mechanism changes, leading to a sped up crack initiation and a loss of sensitivity towards mechanical parameters. The importance of concentration on parameters such as crack density, crack average length and intergranular and transgranular crack velocities was evidenced. Experimental results show that plastic strain is not required for I-SCC crack initiation, if the test time is long enough in the presence of stress. Its main influence is to rush the occurrence of cracking by creating initiation sites, by way of breaking the oxide layer and building up intergranular stress. Below I1, the critical strains at initiation show a substantial strain rate sensitivity. In this domain, a threshold stress of 100 MPa was found, well below the yield stress. Thanks to the combined use of notched specimens and numerical simulations, a strong protective effect of an increasing stress biaxiality ratio was found, both in the elastic and plastic domains. Proton-irradiated samples, up to a dose of 2 dpa, were tested in the same conditions as fresh specimens. The higher I-SCC sensitivity of the irradiated material was measured and the effects of concentration and strain rate were found to remain. Irradiation leads to a higher strain localization causing early crack initiation, but the main reason for the higher sensitivity of the irradiated material seems to be a chemical one, with higher pitting occurrence and a shift of I1.

Carbon nanotubes (CNTs) and gold nanoparticles (AuNPs) are widely used for sensing applications due to their distinctive electrical and optical properties, and we have explored the development of methods that enable the incorporation of these nanomaterials into new and improved sensing devices. As a means for fabricating simple, low-cost and fast detection platforms for various applications, we have developed paper-based electrochemical detection platforms based on CNTs or platinum nanoparticle (PtNP)-CNT composite materials. We describe the use of a paper-based, low density, a three-dimensional thin film of interconnected CNTs as an electrode material. We studied the electrochemical properties of these paper-based CNT electrodes and demonstrated their use as an electrochemical sensor for the sensitive detection of guanine-based nucleotides. We further describe the functionalization of this paper-based electrode by fabricating a PtNP-SWCNT hybrid film via a vacuum filtration-based method. The interconnected PtNP structure formed on top of the CNT-coated paper was directly used as an electrocatalyst for methanol oxidation. Compared to paper-based PtNP-SWCNT hybrid films formed by electrochemical deposition, hybrid films formed by vacuum filtration showed a higher electrochemical surface area and enhanced electrocatalytic response to methanol oxidation. We have also developed methods based around DNA-modified AuNPs, which offer an excellent colorimetric platform for target detection. The DNA density on the surface of modified AuNPs affects enzymatic activity, colloidal stability of AuNPs, the orientation of the probe DNA and its hybridization efficiency. The combination of all these factors ultimately dictates the reaction time and sensitivity of colorimetric assays. We demonstrate the use of DTT as a modulator to control DNA surface coverage on the surface of AuNPs. Using this DTT treatment and a novel probe for exonuclease III activity, we have developed a colorimetric assay based on DTT-treated, DNA-modified AuNPs that can achieve more sensitive and rapid detection of DNA and enzymes relative to existing sensor platforms.

Les propriétés spécifiques des milieux fluides supercritiques sont exploitées depuis denombreuses années dans les domaines de la séparation, de la chimie et des matériaux.Aujourd’hui, les activités de recherche se focalisent vers une meilleure compréhension et unmeilleur contrôle des processus thermodynamiques, physiques et chimiques mis en jeu, ce quinous a naturellement amené à développer la microfluidique supercritique. C’est dans cecontexte que s’inscrivent ces travaux de thèse ayant pour objet le développement et l’utilisationde l’outil microfluidique pour l’étude de la réactivité chimique et de la germination-croissance enmilieux fluides supercritiques.Notre premier objectif a concerné le développement de l’outil microfluidique supercritique etde microsystèmes résistants aux conditions de température et de pression. Quelquescaractéristiques physiques associées à ces dispositifs sont proposées de manière à observerclairement les avantages attendus du couplage de la microfluidique et des fluides supercritiques.Nous avons ensuite validé l’apport de la microfluidique supercritique sur la réactivité chimiqueet la chimie des matériaux via, d’une part, l’étude de l’oxydation hydrothermale du méthanol et,d’autre part, l’élaboration de nanocristaux de ZnO. Les propriétés de photoluminescence de cesnanocristaux de ZnO ont été caractérisées; nous avons montré que l’outil microfluidiquesupercritique permet de synthétiser des nanocristaux de ZnO avec une luminescenceexcitonique. / The unique properties of supercritical fluids (SCFs) have been widely used since the 1980’sin a wide range of applications including separation, chemistry and materials synthesis.Currently, the research activities are focused toward a better understanding and tailoring ofthermodynamical, physical and chemical phenomena involved in SCFs processes. In thiscontext, this is why we have chosen to develop supercritical microfluidics in the frame of thisPhD work, which aims at developing and using microfluidic tools in order to study the chemicalreactivity and the nucleation-growth in supercritical fluids.First of all, our strategy aimed at fabricating microsystems which could handle to the SCFsoperating conditions (high pressure and high temperature). Then, we have studied somephysical characteristics of these devices and in particular we determined the expectedadvantages associated with the combination of microfluidic tools and supercritical fluids.Afterwards, we have demonstrated the benefits of the supercritical microfluidics to materialssynthesis and chemical reactivity through the hydrothermal oxidation of methanol and thesynthesis of ZnO nanocrystals. This last point was also the subject of a photoluminescencestudy, demonstrating that supercritical microfluidics tools can be used as “precision synthesis”reactors.

Uma série de amostras do sistema catalítico V2O5/TiO2 foi preparada pelo método sol-gel com diferentes teores da fase ativa (de 0 a 9% em massa de V2O5) e calcinada em diferentes temperaturas (de 250 a 6000C). Sistema similar foi obtido pelo método de impregnação para a comparação. Os catalisadores foram caracterizados quanto suas propriedades texturais e estruturais pelas técnicas de Adsorção de N2 a 77K, Difratometria de Raios-X (DRX), Espectroscopia Raman, Ressonância Paramagnética Eletrônica (EPR), Espectroscopia de Fotoelétrons Excitados por Raios-X (XPS) e Espectroscopia de Absorção de Raios-X (XAS). Testes catalíticos para a verificação da atividade e seletividade foram realizados frente à reação de conversão do metanol. O sistema obtido pelo método sol-gel apresentou elevada área superficial e porosidade, as quais foram ampliadas com o aumento do teor de vanádio e reduzidos com o aumento da temperatura de calcinação. O sistema preparado por impregnação apresentou as mesmas propriedades texturais do suporte comercial. A análise de DRX identificou a existência de TiO2 nas formas cristalográficas anatásio e rutilo, não foi identificada a presença de V2O5 na forma cristalina. No sistema preparado por impregnação a estrutura cristalográfica do suporte se mantém, independente do teor de vanádio, porém a partir de 6% de V2O5 foi identificado à presença de V2O5 cristalino. Os espectros de Raman mostraram a presença de dois grupos superficiais de vanádio, os vanadilos monoméricos e os vanadatos poliméricos mesmo em elevados teores de vanádio, nos sistemas preparados pelo processo sol-gel. Nos catalisadores obtidos por impregnação foram identificados modos vibracionais referentes ao V2O5 cristalino.Os resultados obtidos por XAS confirmaram os obtidos por DRX e indicaram a presença de vanádio V4+ e V5+, porém com simetria diferente da forma cristalina V2O5. A determinação da razão entre os átomos V/Ti superficiais feita por XPS mostrou ser crescente com o aumento do teor de vanádio. Os espectros de EPR indicaram a presença de pelo menos três famílias de íons V4+ em diferentes simetrias, duas delas inseridas na matriz da titânia na fase rutilo e a outra dispersa na superfície. O sistema obtido por impregnação apresentou poucos íons V4+. Os testes catalíticos revelaram que a atividade e seletividade catalítica foram praticamente as mesmas para os sistemas preparados pelos dois métodos. Entretanto, a estabilidade catalítica do sistema obtido via sol-gel foi superior ao sistema preparado por impregnação. / A series of samples of the catalytic system V2O5/TiO2 was prepared by the sol-gel method with different proportions of the active phase (from 0 to 9% in mass of V2O5) and calcined in different temperatures (from 250 to 6000C). A similar system was obtained by the impregnation method for comparison. The catalyst were characterized by their textural and structural properties by Adsorption of N2 at 77K, X-Ray Diffraction (XRD), Raman Spectroscopy, Electronic Paramagnetic Resonance (EPR), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Absorption Spectroscopy (XAS). Catalytic tests for the verification of the activity and selectivity were performed by the conversion reaction of the methanol. The system obtained by the sol-gel method presented a high superficial area and porosity, which were enlarged by the increase of vanadium proportion and reduced with increase of the calcinations temperature. The system prepared by impregnation presented the same textural proprieties of the commercial support. XRD analysis identified the existence of TiO2 in two crystallographic forms, anatase and rutile. It was not identified the presence of V2O5 in the crystalline form. In the system prepared by impregnation the crystallographic structure of the support keeps, independent of the vanadium content, however starting from 6% of the vanadia was identified crystalline V2O5. Raman spectra showed the presence of two superficial groups of vanadium, the monomeric vanadyls and the polymeric vanadates even for elevated contents of vanadium, in the system prepared by the impregnation method vibrational modes were identified referring to V2O5 crystalline. The results obtained by XAS confirmed the obtained by XRD and indicated the presence of V4+ and V5+, however with different symmetry from the V2O5 in a crystalline form. The determination of the proportion between the surface V/Ti atoms determined by XPS showed to be increased with the increase of the vanadium content. EPR spectra indicated the presence of at least three V4+ion families in different symmetries; two of them inserted in the matrix of titania in the rutile phase and to other dispersed on the surface. The system obtained by impregnation presented few V4+ ions. The catalytic tests reveled that the catalytic activity and selectivity were practically the same for the systems prepared by both methods. However, the catalytic stability of the system obtained via sol-gel was superior to the system prepared by impregnation.

L’utilisation massive de ressources fossiles carbonées pour des applications énergétiques est aujourd’hui pointée du doigt comme responsable du changement climatique. Le CO₂ émis lors de la combustion de ces ressources augmente l’effet de serre, induisant ainsi un réchauffement de la planète. Afin d’atténuer ce changement climatique, l’utilisation des énergies renouvelables est de plus en plus favorisée et le stockage de cette énergie sous forme d’hydrogène semble prometteur pour pallier à l’intermittence saisonnière de ces ressources. Une voie de stockage de l’hydrogène consiste à le faire réagir avec du CO₂ afin d’obtenir des carburants liquides telles que l’acide formique et le méthanol. Ces liquides peuvent alors être transportés facilement et lorsque l’énergie vient à manquer l’hydrogène peut être régénéré par déshydrogénation de ces molécules grâce à des catalyseurs. Dans cette thèse nous avons développé des complexes organométalliques en vue d’activer CO₂ et H₂, ce qui nous a permis d’acquérir un savoir fondamental. Le ligand triphos étant très connu pour coordiner des complexes qui catalysent ces réactions d’hydrogénation et de déshydrogénation, nous nous sommes d’abord concentrés sur le développement de ligands similaires. Nous avons synthétisé de nouveaux complexes de Fe (II), Co (II) et Cu (I) avec ces ligands. Ceux-ci se sont révélés actifs en hydroboration du CO₂. Un complexe de ruthénium a été greffé sur silice par son ligand, afin de pouvoir être recyclé lors des catalyses. Dans une deuxième partie, nous avons synthétisé un nouveau ligand aux des propriétés participatives potentielles. Un complexe de cuivre(I) coordiné par ce ligand a permis d’activer H₂ grâce à une participation métal-ligand.Enfin, un complexe de cobalt(I) coordiné par ce ligand est le premier composé à base de cobalt capable de déshydrogéner l’acide formique. / The extensive use of fossile fuel is currently causing climate change. Anthropogenic emissions of CO₂ enhance the greenhouse effect, resulting in global warming. In order to mitigate this climate change, the share of renewable energy is increasing and hydrogen seems to be a good candidate to stock energy to compensate the seasonal variations of those energies. One way to store H₂ is the hydrogenation of CO₂ to synthesise liquid molecules as formic acid and methanol. Those liquids can be conveyed in an easier way. In case of a lack of energy, H₂ can be recovered through dehydrogenation of those molecules thinks to catalysts. In this thesis, we studied the synthesis of organometallic complexes able to activate those small molecules, thus, growing a fundamental knowledge. As a number of triphos-metal complexes are known to catalyse hydrogenation and dehydrogenation reactions, we focused on the elaboration of ligands alike. With those ligands in hand, several non-noble metal based complexes (Fe (II), Co (II) and Cu (I)) were synthesized, which are active in CO₂ hydroboration catalysis. A complex of ruthenium(II)was grafted on silica through one of this ligand, in order to recycle it when it used as a catalyst. On the second hand, we designed a new ligand which could favor metal-ligand cooperativity. H₂ was succesfully activated with a copper(I) complex coordinated by this ligand, demonstrating that cooperation of the ligand. Finally, the first known cobalt complex active in dehydrogenation of formic acid was synthesised.

As fossil fuel resources become more and more scarce, attention has been turned to alternative sources of fuels and energy. One promising prospect is the conversion of methane (natural gas) to methanol, which requires an initial activation of a C-H bond and subsequent formation of a C-O bond. The most well studied methodologies for both C-H activation and C-O bond formation involve oxidation of the metal center. Metal complexes with facile access to oxidation states separated by four charge units, required for two subsequent oxidations, are rare. Non-oxidative methods to perform C-H bond activation or C-O bond formation must be pursued in order for methane to methanol to become a viable strategy. In this dissertation studies on redox and non-redox methods for both C-H activation and C-O bond formation are discussed. In the early chapters C-O bond formation in the form of reductive functionalization is modeled. Polypyridine ligated rhodium complexes were studied computationally to determine the properties that would promote reductive functionalization. These principles were then tested by designing an experimental complex that could form C-O bonds. This complex was then shown to also work in acidic media, a critical aspect for product stabilization. In the later chapters, non-oxidative C-H activation is discussed with Ir complexes. Both sigma bond metathesis and concerted metalation deprotonation were investigated. For the former, the mechanism for an experimentally known complex was elucidated and for the latter the controlling factors for a proposed catalyst were explored.

This work can be divided into two parts. In the first part, we examine possibilities of preparation of monocrystalline tungsten and tungsten oxide nanoclusters by means of magnetron sputtering with gas aggregation. Clusters are prepared in the non-reactive (Ar) and reactive (Ar + O2) atmosphere and heated after the deposition or during the flight by IR radiation. Influence of oxygen in the aggre- gation process was described and possibilities of generating crystalline tungsten and tungsten oxide clusters were found. In the second part, we study reactivity of tungsten oxide layers, pure and doped with rare metals (Pt, Au), deposited on the silicon wafer and etched carbon, towards partial methanol oxidation. Influence of carbon substrate and metal doppants on reactivity was found and described, along with mofrological and chemical changes that occurs in the sample during the proces. 1