La qualité de l’air extérieur (QAE) a fait l’objet d’une législation dès 1996 avec la loi LAURE. Depuis 2008, la directive européenne 2008/50/CE a instauré des obligations de mesure et de seuils à ne pas dépasser pour certains polluants à l’échelle européenne. Selon de nombreuses données toxicologiques et épidémiologiques, la pollution de l’air est à l’origine d’insuffisances respiratoires, d’asthme, de maladies cardiovasculaires et de cancers.Les composés organiques volatils (COV) et notamment le benzène, le toluène, l’ethylbenzène et les xylènes (les composés BTEX) sont des polluants avérés et participent grandement à la dégradation de la qualité de l’air intérieur et extérieur. Ce travail de thèse a concerné la réalisation d’un multicapteur de gaz à base d’oxyde métallique pour la détection de traces de BTEX dans le cadre du projet SMARTY (SMart AiR qualiTY). Un système de caractérisation électrique complet a été conçu et mise au point pour la détection de très faibles concentrations de BTEX (le ppb). Après une étude bibliographique, plusieurs matériaux ont été sélectionnés (WO3, ZnO, SnO2). Les caractérisations électriques des couches sensibles sélectionnées ont été effectuées sous air sec et sous différents taux d’humidité en présence de BTEX et de gaz interférents (NO2, CO2). Le WO3 a montré les meilleures performances en présence d’humidité et a été choisi pour le transfert de technologie qui accompagne les nouveaux transducteurs brevetés AMU. Le multicapteur à base de WO3 a montré une détection limite de 1 ppb sous 50% d’humidité relative et a permis de détecter et de quantifier de manière efficace les BTEX. / Outdoor air quality is subjected to the law LAURE since 1996. In 2008, the european directive 2008/50/EC introduced measurement requirements and thresholds that should not be exceeded for certain pollutants on a european scale. According to several toxicological and epidemiological studies, air pollution causes respiratory failure, asthma, cardiovascular diseases and cancers. In Europe, air pollution is responsible for more than 300 000 early deaths a year.Volatile organic compounds (VOCs), particularly benzene, toluene, ethylbenzene and xylenes (BTEX compounds) are proven pollutants and play a major role in the degradation of indoor and outdoor air quality. This thesis is dedicated to the development of a metal oxide based multi-gas sensor for the detection of traces of BTEX within the framework of the SMARTY project (SMart AiR qualiTY). A complete electrical characterization system was designed and implemented for the detection of sub-ppm concentrations of BTEX.Based on the state-of-art, several materials were selected (WO3, ZnO, SnO2). The electrical characterizations of the selected sensitive layers were carried out under dry air and under different humidity levels in the presence of BTEX and interfering gases (NO2, CO2). Tungsten oxide (WO3) exhibits the best performance in the presence of moisture and is chosen for the technology transfer that accompanies the new patented AMU transducers. The WO3-based multi-sensor has a lower limit of detection (LOD) of 1 ppb at 50% relative humidity and effectively detects and quantifies BTEX.

Les systèmes électrochromes, dont les propriétés optiques changent sous l’effet d’une excitation électrique, suscitent un intérêt croissant dû au fait qu’ils permettent un contrôle des propriétés optiques dans le domaine du visible et du proche infrarouge. Le but, initié dans des travaux précédents, vise à optimiser la synthèse, par pulvérisation cathodique magnétron, de films minces d’une épaisseur de 300 nm pouvant être intégrés dans un futur dispositif électrochrome « tout céramique » à conduction de sodium. Dans ce travail de thèse, deux matériaux constituant ce dispositif ont été étudiés. Le premier concerné est l’oxyde de tungstène, connu pour servir de couche électrochrome dans les dispositifs. Les couches synthétisées possèdent des propriétés de conduction mixte, une structure amorphe et une morphologie poreuse permettant l’intercalation de cations de sodium Na+ en son sein. Une dégradation du film de WO3 due à une réactivité rédhibitoire vis-à-vis de l’eau a été observée. Pour éliminer cela, deux solutions ont été testées : un cyclage en milieu non aqueux ou le recouvrement du film par un électrolyte solide de type NaSICon. La stoechiométrie en oxygène des films, a permis de régler la conductivité électronique, l’absorption dans le visible et la capacité des films à échanger des ions Na+. Le second matériau étudié est un oxyde de tungstène pré-inséré en sodium NaxWOy. L’influence des conditions de synthèse et celle de la teneur en sodium sur les différentes propriétés des films a été étudiée. Ces propriétés ont ensuite été comparées à celles obtenues pour les films de WO3 et pour des bronzes de tungstène NaxWO3 reportées dans la littérature. / Electrochromic systems, whose optical properties change under the effect of an electrical excitation, see an increasing interest because they allow a control of optical properties in the visible and near infrared. The aim, initiated in previous works, is to optimize the synthesis of 300 nm thin films by magnetron sputtering to be integrated into a future electrochromic "all ceramic" device based on sodium conduction. In this PhD, two materials forming the system have been studied. The first material is the tungsten oxide, known to serve as the electrochromic layer in devices. The synthesized layers possess mixed conducting properties, an amorphous structure and a porous morphology allowing the intercalation of sodium cations. A degradation of the WO3 film due to redhibitory reactivity towards water was observed. To eliminate this reactivity, two solutions were tested: a non-aqueous cycling or covering of the initial film by depositing a solid electrolyte of the type NaSICon. The oxygen stoichiometry of the films, allowed to tune the electronic conductivity, the absorption in the visible and the ability of the film to exchange Na+ cations. The second studied material is a pre-inserted NaxWOy sodium tungsten oxide. The influence of the synthesis conditions and of the sodium content on the various properties of the films was investigated. These properties were then compared with those obtained for the WO3 films and those of NaxWO3 tungsten bronzes reported in the literature.

Il est couramment admis que le niveau de pollution dans l'environnement intérieur pouvait dépasser le niveau de pollution extérieur. C’est la raison pour laquelle la qualité de l'air intérieur est devenue une préoccupation sociétale importante en raison de la durée croissante que nous passons dans ces environnements. Les procédés d'oxydation avancée (POA), parmi lesquels l'oxydation photocatalytique, sont des techniques pertinentes pour la purification de l'air. En photocatalyse, les nanotubes de titane montrent un intérêt tout particulier en raison de leurs propriétés intrinsèques spécifiques de par leurstructure tubulaire. Ce matériau unidimensionnel engendre un rapport surface/volume important qui donne accès à une surface spécifique et à des capacités d’adsorption importantes, mais aussi à des propriétés de transport électronique accrues. Deux molécules modèles gazeuses ont été retenues, la méthyléthylcétone (MEC) et le sulfure de dihydrogène (H2S). Ces molécules diffèrent de par leur composition chimique (présence ou non d’hétéroatomes) et leurs propriétés physico-chimiques et reflètent différentes catégories de pollutions chimiques et olfactives. Afin d’améliorer les performances photocatalytiques des nanotubes, de TiO2 synthétisés par méthode hydrothermale, que ce soit sous illumination UV-A ou solaire, des modifications avec un autre semi-conducteur WO3 ou ZnO ont été entreprises. Les mêmes modifications ont également été réalisées sur le photocatalyseur commercial TiO2 P25 (Evonik). Une des finalités de ce travail est la corrélation des conditions de synthèse de ces matériaux avec leurs caractéristiques physico-chimiques et avec leurs propriétés photocatalytiques vis-àvis de l’élimination des deux polluants étudiés. Une approche mécanistique a également été menée. / Indoor air quality has become an important social concern due to the increased amount of time spent in indoor environment. It is now well admitted that the pollution level in indoor environment could exceed the pollution level outdoor. Advanced Oxidation Processes (AOP), such as photocatalytic oxidation, are promising technologies for air purification. The synthesis and applications of high aspect ratio onedimensional titania-based nanostructures have attracted increasing attention. In photocatalysis, titania nanotubes have already shown enhanced photocatalytic efficiency over nanoparticles, enabled by highersurface area, tubular structure with higher charge carriers generation and transfer efficiency. However, together with visible light activation, higher efficiency is a challenging task. The fundamental challenges are to develop controlled and self-assembled 1D-TiO2-based nanostructures for improving the light absorption, generation and transfer of electrons and specific surface area. In this thesis, two model gas molecules were used, methyl ethyl ketone (MEK) and dihydrogen sulfide (H2S). These molecules differ in their chemical composition (presence or absence of heteroatoms) and their physico-chemical properties and reflect different types of chemical and odor pollutions. In order to improve the photocatalyticperformance of TiO2 nanotubes synthesized by the hydrothermal method, either under UV-A or solar illumination, modifications with another semiconductor, WO3 or ZnO, were made. The same modifications were also made on the commercial photocatalyst TiO2 P25 (Evonik). One of the aims of this study is the correlation of synthesis conditions of these materials with their physico-chemical properties and their photocatalytic properties regarding the elimination of the two pollutants studied. A mechanistic approach was also conducted.

Ce travail de thèse porte sur l’amélioration des performances des capteurs de gaz à base de WO3 en s’intéressant particulièrement à l’effet de l’ajout des nanoparticules métalliques sur les propriétés de détection de ces dispositifs. La démarche a consisté à évaluer puis améliorer les performances des capteurs sous différents gaz oxydants et réducteurs. Deux approches ont été menées : une approche théorique qui consiste à modéliser la résistance du capteur sous gaz et une approche expérimentale qui consiste à modifier la surface des couches sensibles par des ajouts métalliques. Le modèle ainsi développé a permis de mettre en évidence les différents paramètres intrinsèques et structuraux de la couche sensible, sur lesquels il est possible d’agir pour améliorer les performances des capteurs. La deuxième approche a consisté à ajouter des nanograins métalliques. Cette méthode montre une grande efficacité sur les performances des capteurs. Les résultats obtenus avec les nanoparticules d’or montrent en effet une amélioration de la réponse, des temps de réponse et de recouvrement ainsi que du temps de stabilisation des capteurs sous ozone. Il en est de même pour les ajouts de nanoparticules d’argent et de palladium, même si les résultats sont différents. Dans le cas de l’ajout de nanoparticules de cobalt, un phénomène singulier se manifeste par l’inversion des réponses des capteurs dans certains cas. Cette propriété peut être exploitée pour la détection sélective de différents gaz, avec la même couche sensible modifiée par l’ajout de très faibles quantités de matière. / This work focuses on improving the performance of WO3-based gas sensors with particular attention to the effect of metal additives on device sensing properties. The goal is to assess and improve the performance of sensors under different oxidizing and reducing gases. Two approaches have been taken: a theoretical approach which consists in the modeling of gas sensor resistance and an experimental approach which consists in modifying the surface of the sensitive layers by metal nanograins. The developed model allowed us to highlight the various intrinsic and structural parameters of the sensitive layer, in which it is possible to act to improve the performance of the sensors. The second approach is to add metallic nanograins. This method shows high efficiency on the sensor performance. Indeed, the results obtained with the gold nanoparticles show improved response, response and recovery times, and the time stabilization under ozone. It is the same for the additions of silver and palladium nanoparticles, even if the results are different. In the case of adding cobalt nanoparticles, a singular phenomenon is manifested by the sensor responses inversion in some cases. This property can be exploited for the selective detection of different gases, with the same sensitive layer modified by the addition of very small quantities of material.

Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 WilliamGM_DISSERT.pdf: 1986302 bytes, checksum: 71e6a449a8f77e2f64a9c3908ab5410d (MD5) Previous issue date: 2013-07-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / A new self-sustainable film was prepared through the sol-gel modified method, previously employed in our research group; sodium alginate was used as the polymer matrix, along with plasticizer glycerol, doped with titanium dioxide (TiO2) and tungsten trioxide (WO3). By varying WO3 concentration (0,8, 1,6, 2,4 and 3,2 μmol) and keeping TiO2 concentration constant (059 mmol), it was possible to study the contribution of these oxides on the obtained films morphological and electrical properties. Self-sustainable films have analyzed by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XDR), Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS) and Electrochemical Impedance Spectroscopy (EIS). By the IR specters, it was possible identify the TiO2, and posteriorly WO3, addition has provided dislocation of alginate characteristics bands to smaller vibrations frequencies indicating an electrostatic interaction between the oxides and the polymer matrix. Diffractograms show predominance of the amorphous phase in the films. SEM, along with EDX, analysis revealed self-sustainable films showed surface with no cracks and relative dispersion of the oxides throughout the polymer matrix. From Impedance analysis, it was observe increasing WO3 concentration to 2,4 μmol provided a reduction of films resistive properties and consequent improvement of conductive properties / Um novo filme autossustent?vel foi preparado, atrav?s do m?todo sol-gel modificado, anteriormente empregado no nosso grupo de pesquisa, utilizando como matriz polim?rica o alginato de s?dio, juntamente com o plastificante glicerol, dopado com di?xido de tit?nio (TiO2) e tri?xido de tungst?nio (WO3). Variando as concentra??es do WO3 (0,8, 1,6, 2,4 e 3,2 μmol), e mantendo constante a concentra??o do TiO2 (0,59 mmol), foi poss?vel estudar a contribui??o destes ?xidos nas propriedades morfol?gicas e el?tricas dos filmes obtidos. Os filmes autossustent?veis foram caracterizados atrav?s das t?cnicas de Espectroscopia de Infravermelho com Transformada de Fourier (FTIR), Difratometria de Raios X (DRX), Microscopia Eletr?nica de Varredura (MEV), Espectroscopia de Raios X por Dispers?o de Energia (EDS) e Espectroscopia de Imped?ncia Eletroqu?mica (EIE). Atrav?s dos espectros de FTIR foi poss?vel identificar que a adi??o do TiO2 e, posteriormente, do WO3 proporciona deslocamento das bandas caracter?sticas do alginato para menores frequ?ncias de vibra??o, indicando uma intera??o eletrost?tica dos ?xidos com a matriz polim?rica. Os difratogramas evidenciaram a predomin?ncia do comportamento amorfo nos filmes. As an?lises de MEV, juntamente com as de EDS, revelaram que os filmes autossustent?veis apresentam uma superf?cie sem trincamento e de relativa dispers?o dos ?xidos ao longo da matriz polim?rica. Atrav?s da EIE observouse que o aumento da concentra??o de WO3 at? 2,4 μmol proporcionou uma redu??o do comportamento resistivo dos filmes, e consequente melhoria em suas propriedades condutoras

Tecnologias efetivas para o tratamento de águas e efluentes representam um dos grandes desafios da nossa sociedade; dentre as opções, a fotoeletrocatálise pode ser considerada como uma técnica alternativa e de interesse. Nesse contexto, o presente trabalho teve como objetivo desenvolver eletrodos de TiO2 modificados visando o tratamento fotoeletrocatalítico de interferentes endócrinos. Realizou-se inicialmente a síntese de nanotubos de TiO2 (TiO2-NT) sobre substrato de Ti metálico via anodização eletroquímica em eletrólito NaH2PO4/HF. Para minimizar as limitações inerentes ao TiO2 realizou-se a eletrodeposição de WO3 sobre os nanotubos de TiO2 (Ti/TiO2-NT/WO3) e diretamente sobre o substrato de Ti metálico. Este último revelou a formação de uma camada fina de TiO2 sobre a superfície, posterior ao tratamento térmico, formando um compósito (Ti/TiO2/WO3). A análise de difração de raios-X confirmou a formação da fase monoclínica de WO3 para ambas as sínteses e a fase anatase para os eletrodos de Ti/TiO2-NT/WO3. Para as duas sínteses, as medidas de energia dispersiva de raios-X revelaram uma quantidade crescente de W na composição dos eletrodos com o aumento do tempo de eletrodeposição. Teores elevados de W (acima de 1,2 %) apresentaram uma diminuição expressiva nos valores de fotocorrente. No entanto, baixos teores de W (entre 0,4 e 1,2 %) indicaram um aumento de 20 % nos valores de fotocorrente para os eletrodos de Ti/TiO2-NT/WO3 (20 mA cm-2) e Ti/TiO2/WO3 (17 mA cm-2) comparados aos não modificados, no potencial de +2,0 V. As análises de reflectância difusa mostraram uma baixa energia de bandgap (≈ 2,90 eV, eletrodos de Ti/TiO2-NT/WO3) e um aumento na absorção da irradiação UV-Vis. Posteriormente, os eletrodos modificados foram aplicados na oxidação fotoeletrocatalítica (FE) dos compostos bisfenol-A (BPA) e propilparabeno (PPB), sob irradiação UV-Vis. O método FE apresentou um excelente desempenho em condições ácidas, aplicando-se potencial de +1,50 V e +0,50 V para os eletrodos Ti/TiO2-NT/WO3 e Ti/TiO2/WO3, respectivamente. A mineralização dos compostos BPA e PPB foi superior a 80 % tanto para o Ti/TiO2-NT/WO3 como para o Ti/TiO2/WO3. Quanto à taxa de remoção, o BPA e PPB foram completamente removidos após 45 e 60 min, respectivamente, para os eletrodos de Ti/TiO2/WO3 e após 30 minutos para os eletrodos de Ti/TiO2-NT/WO3. Adicionalmente, os eletrodos apresentaram um baixo consumo energético e boa estabilidade química. Comparada à técnica de fotocatálise (FC), a FE revelou uma eficiência de mineralização 2 vezes superior para o Ti/TiO2-NT/WO3 e mais de 20 % superior para o Ti/TiO2/WO3. Logo, as modificações dos eletrodos de TiO2 com WO3 constituíram importantes contribuições para o desempenho dos materiais, sendo um passo importante para a aplicação em tratamentos alternativos de descontaminação de águas residuárias. Ainda foi de interesse neste trabalho propor um método para a inserção de nanotubos (TiNT) e nanofolhas (TiNS) de titanatos no interior de nanotubos de TiO2 via eletroforese. O estudo possibilitou o desenvolvimento de um método simples e eficiente para a modificação de nanoestruturas complexas. A movimentação do contra eletrodo sobre a superfície do eletrodo de trabalho, adaptado com uma escova nas laterais, reduziu a espessura da camada de TiNS/TiNT. O potencial aplicado (20 V) e a estimulação mecânica da superfície foram importantes para a incorporação das nanoestruturas dentro dos poros de TiO2-NTs. Como resultado, os eletrodos apresentaram um aumento da hidrofobicidade e uma melhora na capacidade de oxidação direta comparado ao eletrodo não modificado. / Effective technologies for the water and wastewater treatment represent a challenges for our society; among the options, the photoelectrocatalysis can be considered a promising and interesting alternative. In this context, the objective of this study was to develop modified TiO2 electrodes for the photoelectrocatalytic treatment of endocrine disruptors. The synthesis of TiO2 nanotubes (TiO2-NT) on metallic Ti substrate was carried out via electrochemical anodization in NaH2PO4 /HF electrolyte. In order to minimize the limitations inherent of TiO2, the electrodeposition of WO3 was performed on the TiO2 nanotubes (Ti/TiO2-NT/WO3) and also in the metallic Ti substrate. The deposition on the Ti metallic produced a thin layer of TiO2 on the surface, subsequent to the heat treatment, generating a composite (Ti/TiO2/WO3). The X-ray diffraction analysis (XRD) confirmed the monoclinic phase of WO3 for both the syntheses and the anatase phase of TiO2 for the Ti/TiO2-NT/WO3 electrodes. For the two syntheses, the X-ray dispersive energy (EDX) analisys indicated an increasing amount of tungsten (W) in the composition of the electrodes with increasing of electrodeposition time. High W content (above 1.2%) showed a significant decrease in the photocurrent values. However, low content of W (between 0.4 and 1.2 %) indicated an increase of 20 % in the photocurrent values for the electrodes Ti/TiO2-NT/WO3 (20 mA cm-2) and Ti/TiO2/WO3 (17 mA cm-2) compared to the unmodified ones, at the potential of +2.0 V. Difuse reflectance analysis indicated low bandgap energy (≈ 2.90 eV, Ti/TiO2-NT/WO3 electrodes) and an increase in the UV-Vis irradiation absorption. The best electrodes modified with WO3 to the both syntheses were applied in the photoelectrocatalytic oxidation (PEC) of bisphenol-A (BPA) and propylparaben (PPB) compounds, under UV-Vis irradiation. The PEC method presented an excellent performance in acidic conditions, applying a bias potential of +1.50 V and +0.50 V for Ti/TiO2-NT/WO3 and Ti/TiO2/WO3 electrodes, respectively. The mineralization of BPA and PPB compounds was greater than 80% for both Ti/TiO2-NT/WO3 and Ti/TiO2/WO3. In relation to the removal rate, BPA and PPB were completely removed after 45 and 60 min, respectively, for Ti/TiO2/WO3 electrodes and after 30 minutes for Ti/TiO2-NT/WO3 electrodes. Additionally, the electrodes presented a low energy consumption and good chemical stability. Compared to the photocatalysis (PC), the PEC was 2 times higher to the mineralization efficiency for Ti/TiO2-NT/WO3 and almost 20% higher for Ti/TiO2/WO3. Thus, the modifications of the TiO2 electrodes with WO3 represent an important contribution to the performance of materials and, therefore, a positive step for the application in alternative treatments of decontamination of wastewater. It was also of interest in this work to propose a new method for the insertion of nanotubes (TiNT) and nanosheets (TiNS) of titanates inside of TiO2 nanotubes via electrophoretic deposition. In this study was developed a simple and efficient method for the modification of complex nanostructures. The movement of the counter electrode on the surface of the working electrode, adapted with a brush on the edges, reduced the thickness of the TiNS/TiNT layer. The potential applied (20 V) and the mechanical stimulation in the surface were important for the incorporation of TiNS/TiNT into the pores of TiO2-NTs. As a result, the electrodes increased the hydrophobicity and an improvement to the direct oxidation capacity compared to the unmodified electrode.

Tecnologias efetivas para o tratamento de águas e efluentes representam um dos grandes desafios da nossa sociedade; dentre as opções, a fotoeletrocatálise pode ser considerada como uma técnica alternativa e de interesse. Nesse contexto, o presente trabalho teve como objetivo desenvolver eletrodos de TiO2 modificados visando o tratamento fotoeletrocatalítico de interferentes endócrinos. Realizou-se inicialmente a síntese de nanotubos de TiO2 (TiO2-NT) sobre substrato de Ti metálico via anodização eletroquímica em eletrólito NaH2PO4/HF. Para minimizar as limitações inerentes ao TiO2 realizou-se a eletrodeposição de WO3 sobre os nanotubos de TiO2 (Ti/TiO2-NT/WO3) e diretamente sobre o substrato de Ti metálico. Este último revelou a formação de uma camada fina de TiO2 sobre a superfície, posterior ao tratamento térmico, formando um compósito (Ti/TiO2/WO3). A análise de difração de raios-X confirmou a formação da fase monoclínica de WO3 para ambas as sínteses e a fase anatase para os eletrodos de Ti/TiO2-NT/WO3. Para as duas sínteses, as medidas de energia dispersiva de raios-X revelaram uma quantidade crescente de W na composição dos eletrodos com o aumento do tempo de eletrodeposição. Teores elevados de W (acima de 1,2 %) apresentaram uma diminuição expressiva nos valores de fotocorrente. No entanto, baixos teores de W (entre 0,4 e 1,2 %) indicaram um aumento de 20 % nos valores de fotocorrente para os eletrodos de Ti/TiO2-NT/WO3 (20 mA cm-2) e Ti/TiO2/WO3 (17 mA cm-2) comparados aos não modificados, no potencial de +2,0 V. As análises de reflectância difusa mostraram uma baixa energia de bandgap (≈ 2,90 eV, eletrodos de Ti/TiO2-NT/WO3) e um aumento na absorção da irradiação UV-Vis. Posteriormente, os eletrodos modificados foram aplicados na oxidação fotoeletrocatalítica (FE) dos compostos bisfenol-A (BPA) e propilparabeno (PPB), sob irradiação UV-Vis. O método FE apresentou um excelente desempenho em condições ácidas, aplicando-se potencial de +1,50 V e +0,50 V para os eletrodos Ti/TiO2-NT/WO3 e Ti/TiO2/WO3, respectivamente. A mineralização dos compostos BPA e PPB foi superior a 80 % tanto para o Ti/TiO2-NT/WO3 como para o Ti/TiO2/WO3. Quanto à taxa de remoção, o BPA e PPB foram completamente removidos após 45 e 60 min, respectivamente, para os eletrodos de Ti/TiO2/WO3 e após 30 minutos para os eletrodos de Ti/TiO2-NT/WO3. Adicionalmente, os eletrodos apresentaram um baixo consumo energético e boa estabilidade química. Comparada à técnica de fotocatálise (FC), a FE revelou uma eficiência de mineralização 2 vezes superior para o Ti/TiO2-NT/WO3 e mais de 20 % superior para o Ti/TiO2/WO3. Logo, as modificações dos eletrodos de TiO2 com WO3 constituíram importantes contribuições para o desempenho dos materiais, sendo um passo importante para a aplicação em tratamentos alternativos de descontaminação de águas residuárias. Ainda foi de interesse neste trabalho propor um método para a inserção de nanotubos (TiNT) e nanofolhas (TiNS) de titanatos no interior de nanotubos de TiO2 via eletroforese. O estudo possibilitou o desenvolvimento de um método simples e eficiente para a modificação de nanoestruturas complexas. A movimentação do contra eletrodo sobre a superfície do eletrodo de trabalho, adaptado com uma escova nas laterais, reduziu a espessura da camada de TiNS/TiNT. O potencial aplicado (20 V) e a estimulação mecânica da superfície foram importantes para a incorporação das nanoestruturas dentro dos poros de TiO2-NTs. Como resultado, os eletrodos apresentaram um aumento da hidrofobicidade e uma melhora na capacidade de oxidação direta comparado ao eletrodo não modificado. / Effective technologies for the water and wastewater treatment represent a challenges for our society; among the options, the photoelectrocatalysis can be considered a promising and interesting alternative. In this context, the objective of this study was to develop modified TiO2 electrodes for the photoelectrocatalytic treatment of endocrine disruptors. The synthesis of TiO2 nanotubes (TiO2-NT) on metallic Ti substrate was carried out via electrochemical anodization in NaH2PO4 /HF electrolyte. In order to minimize the limitations inherent of TiO2, the electrodeposition of WO3 was performed on the TiO2 nanotubes (Ti/TiO2-NT/WO3) and also in the metallic Ti substrate. The deposition on the Ti metallic produced a thin layer of TiO2 on the surface, subsequent to the heat treatment, generating a composite (Ti/TiO2/WO3). The X-ray diffraction analysis (XRD) confirmed the monoclinic phase of WO3 for both the syntheses and the anatase phase of TiO2 for the Ti/TiO2-NT/WO3 electrodes. For the two syntheses, the X-ray dispersive energy (EDX) analisys indicated an increasing amount of tungsten (W) in the composition of the electrodes with increasing of electrodeposition time. High W content (above 1.2%) showed a significant decrease in the photocurrent values. However, low content of W (between 0.4 and 1.2 %) indicated an increase of 20 % in the photocurrent values for the electrodes Ti/TiO2-NT/WO3 (20 mA cm-2) and Ti/TiO2/WO3 (17 mA cm-2) compared to the unmodified ones, at the potential of +2.0 V. Difuse reflectance analysis indicated low bandgap energy (≈ 2.90 eV, Ti/TiO2-NT/WO3 electrodes) and an increase in the UV-Vis irradiation absorption. The best electrodes modified with WO3 to the both syntheses were applied in the photoelectrocatalytic oxidation (PEC) of bisphenol-A (BPA) and propylparaben (PPB) compounds, under UV-Vis irradiation. The PEC method presented an excellent performance in acidic conditions, applying a bias potential of +1.50 V and +0.50 V for Ti/TiO2-NT/WO3 and Ti/TiO2/WO3 electrodes, respectively. The mineralization of BPA and PPB compounds was greater than 80% for both Ti/TiO2-NT/WO3 and Ti/TiO2/WO3. In relation to the removal rate, BPA and PPB were completely removed after 45 and 60 min, respectively, for Ti/TiO2/WO3 electrodes and after 30 minutes for Ti/TiO2-NT/WO3 electrodes. Additionally, the electrodes presented a low energy consumption and good chemical stability. Compared to the photocatalysis (PC), the PEC was 2 times higher to the mineralization efficiency for Ti/TiO2-NT/WO3 and almost 20% higher for Ti/TiO2/WO3. Thus, the modifications of the TiO2 electrodes with WO3 represent an important contribution to the performance of materials and, therefore, a positive step for the application in alternative treatments of decontamination of wastewater. It was also of interest in this work to propose a new method for the insertion of nanotubes (TiNT) and nanosheets (TiNS) of titanates inside of TiO2 nanotubes via electrophoretic deposition. In this study was developed a simple and efficient method for the modification of complex nanostructures. The movement of the counter electrode on the surface of the working electrode, adapted with a brush on the edges, reduced the thickness of the TiNS/TiNT layer. The potential applied (20 V) and the mechanical stimulation in the surface were important for the incorporation of TiNS/TiNT into the pores of TiO2-NTs. As a result, the electrodes increased the hydrophobicity and an improvement to the direct oxidation capacity compared to the unmodified electrode.

Dans ce travail, nous étudions la stabilité thermique et les effets des irradiations par un plasma d'hélium ou de deutérium de films minces de WO3 d’intérêt pour la fusion magnétique (projet ITER). L’objectif est de comprendre comment une oxydation du divertor modifie les interactions plasma paroi. Pour cela, nous avons synthétisé des films de WO3 par oxydation thermique de substrats de W à 400°C et caractérisé les effets du type de substrat, de la pression d’oxygène et du temps d’oxydation sur la structure et sur l’épaisseur des oxydes formés. La structure (monoclinique nanocristalline), la morphologie et les défauts des échantillons ont été analysés avant et après traitement, à différentes échelles, en utilisant la microscopie électronique, la microscopie Raman, la diffraction de rayons X, et la microscopie à force atomique.Le chauffage sous vide (400 - 800°C) a conduit à la formation de WO2. Le bombardement aux ions D+ (11 eV) a mené à une diffusion profonde du deutérium à travers le film d’oxyde, engendrant un effet électrochimique, observé ici pour la première fois sous irradiation plasma. Cet effet, réversible, est associé à la formation de bronzes de tungstène (DxWO3) et à une transition de phase vers une structure hexagonale. Des bombardements aux ions He+ (20 eV) ont été réalisés afin de dissocier les effets physiques et chimiques. A température ambiante, le bombardement a causé peu de changements morphologiques et structuraux. Par contre, le autre bombardement à 400°C a causé une érosion du film d’oxyde accompagnée d’un changement de couleur, une amorphisation en surface et la formation de bulles à l’interface W / WO3. / As part of laboratory studies devoted to magnetic fusion we have investigated the thermal stability and the effects of helium and deuterium plasma irradiation on tungsten oxide thin films. The objective is to predict the consequences of the oxidation of the W plasma facing component (divertor) for plasma wall interactions.To this aim, we have synthesized WO3 films by thermal oxidation of W substrates at 400°C and we have characterized the effects of the W substrate, the oxygen pressure and the oxidation duration on the structure and the thickness of the oxide films. The sample crystalline structure (monoclinic nanocrystalline), defects and morphologies were characterized before and after treatment using scanning and transmission electron microscopies, Raman microscopy, X-Ray diffraction and atomic force microscopy. Heating under vacuum up to 800°C leads to changes in the film structure and composition which results in the formation of WO2. D+ bombardment (11 eV) leads to D+ diffusion throughout the oxide film and to an electrochromic effect, here observed for the first time under plasma irradiation. This effect - which turned out to be reversible - is related to the formation of W bronzes (DxWO3) and to a phase transition of the oxide toward a hexagonal structure. Helium bombardments (20 eV) have then been performed to unravel physical and chemical processes at play. He+ bombardment at room temperature causes slight structural and morphological changes. On the contrary, He+ bombardment at 400°C leads to a significant erosion of the oxide film, accompanied by a colour change, the surface amorphisation and the formation of bubbles at the W / WO3 interface.

La présente étude a pour objectif l'obtention d'une équation donnant la vitesse globale de la réaction (activité catalytique) de la réaction NH3-SCR sur des catalyseurs du type V2O5/WO3/TiO2 (a) utilisable pour des conditions expérimentales (pressions partielles des réactifs et des constituants du mélange gazeux et températures) réalistes des conditions des rejets gazeux des centrales à charbon et (b) capable de rendre compte des effets d'empoisonnements chimiques du catalyseur. Cette équation sera implantée dans un logiciel de modélisation de l'évolution des performances des catalyseurs industriels développé par EDF. Pour remplir ces objectifs, les outils et les procédures pour l'approche microcinétique expérimentale ont été appliqués. La caractérisation de la première étape clé qui consiste à adsorbé le réactif NH3 à la surface du catalyseur (type d'adsorption, chaleurs d'adsorption de chaque espèce) a nécessité le développement de la méthode AEIR (initialement adaptée à la caractérisation de CO adsorbé sur des particules métalliques). La réactivité des espèces NH3 adsorbées vis-à-vis des différents réactifs (H2O, NOx, O2) a ensuite été étudiée, conduisant à l'élaboration d'un mécanisme cinétique plausible. A partir de ce mécanisme, un modèle cinétique de la réaction NH3-SCR a été développé et comparé aux données expérimentales obtenues sur catalyseurs modèles et commerciaux. Dans la suite de l'étude, les impacts de plusieurs poisons sur les paramètres contrôlant la cinétique de la réaction ont été déterminés expérimentalement. Dans une dernière partie, un modèle permettant de modéliser les performances catalytique de monolithes a été développé (en intégrant le modèle cinétique mis en place au cours de cette étude) et comparé à des données expérimentales / The aim of the study is to obtain an equation for the overall reaction rate of the NH3-SCR reaction over V2O5/WO3/TiO2 catalysts (a) used for the experimental conditions (partial pressure of components of the gas mixture and temperature) realistic conditions of discharges from coal power plant and (b) able to take into account the chemical poisoning effects of the catalyst. This equation will be implemented in software developed by EDF for modeling the evolution of the performance of industrial catalysts. To fulfill these objectives, tools and procedures for the experimental microkinetic approach were applied. The characterization of the first key step of the reagent adsorbed NH3 on the surface of catalyst (type adsorption, heats of adsorption of each species) has necessitated the development of the AEIR method (initially adapted to the characterization of CO adsorbed on metal particles). The reactivity of the NH3 adsorbed species to the various reagents (H2O, NOx, and O2) was then studied, leading to the development of plausible kinetic mechanism. From this mechanism, a kinetic model of the NH3-SCR reaction has been developed and compared to experimental data obtained on model and commercial catalysts. In the remainder of the study, the impacts of several poisons to parameters that control the kinetics of the reaction were determined experimentally. In the last part, a model of catalytic monoliths performances was developed (by integrating the kinetic model developed in this study) and compared to experimental data

This diploma thesis deals with milling of dispersed particles of WO3 using low-cost wet ball milling. Thin layers of WO3 were formed from them. These layers were characterized by profilometry, turbidity measurements, XRD and SEM. The photocatalytic activity was studied by the electrocatalytic properties of these layers. Profilometric measurements showed declining trends with milling time. XRD measurements confirmed the milling process and revealed a change in the crystalline phase during this process. Electrophotocatalytic measurements confirmed the photocatalytic activity of these layers and revealed its trends.