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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
221

Interfacing Biomolecules with Nanomaterials for Novel Applications

Lal, Nidhi January 2014 (has links) (PDF)
This thesis deals with the research work carried out for the development of novel applications by integrating biomolecules with various nanostructures. The thesis is organized as follows: Chapter 1 reviews the properties of nanomaterials which are important to consider while developing them for various biological and other applications. It discusses the factors which affect the cytotoxicity of nanocrystals towards living cells, photocatalytic mechanisms of nanocrystals that work behind the inactivation of bacterial cells and gas sensing properties of nanocrystals. It also mentions about the integration of biomolecules with nanomaterials which is useful for the development of biosensors, materials that are presently used for fabricating biosensors and the challenges associated with designing successful biosensors. Chapter 2 presents the antibacterial and anticancer properties of ZnO/Ag nanohybids. In this study a simple route to synthesize ZnO/Ag nanohybrids by microwave synthesis has been established where ZnO/Ag nanohybrids have shown synergistic cytotoxicity towards mammalian cells. The observed synergism in the cytotoxicity of ZnO/Ag nanohybrids could lead to the development of low dose therapeutics for cancer treatment. Chapter 3 presents photocatalytic inactivation of bacterial cells by pentavalent bismuthates class of materials. AgBiO3 which was obtained from KBiO3 by ion-exchange method was investigated for its photocatalytic inactivation properties towards E.coli and S.aureus cells under dark and UV illumination conditions. Chapter 4 presents the integration of DNA molecules with ZnO nanorods for the observation of Mott-Gurney characteristics. In this study, ZnO nanorods were synthesized hydrothermally and were characterized by TEM and XRD analysis. DNA molecules were immobilized over ZnO nanorods which were confirmed by UV-Vis spectroscopy and confocal florescence microscopy. Solution processed devices were fabricated by using these DNA immobilized nanostructures and I-V characteristics of these devices were taken in dark and under illumination conditions at different wavelengths of light at fixed intensity. Interestingly, Mott-Gurney law was observed in the I-V characteristics of the devices fabricated using DNA immobilized ZnO nanorods. Chapter 5 presents the chemical synthesis of molecular scale ultrathin Au nanowires. These nanostructures were then used for fabricating electronic biosensors. In this study, the devices were fabricated over Au nanowires by e-beam lithography and a methodology to functionalize Au nanowires and then characterize them by florescence microscopy as well as AFM has been established. The fabricated biosensors were employed for the label free, electrical detection of DNA hybridization process. Chapter 6 presents a simple, cost effective and solution processed route to fabricate devices using ultrathin Au nanowires. The devices were then used for sensing ethanol, H2 and NH3. An important property of these devices is that they can sense these gases at room temperature which reduce their operation cost and makes them desirable to use under explosive conditions.
222

Etude des moyens de lithographie haute résolution pour la fabrication de résonateurs à ondes élastiques de surface : application aux sources embarquées / Study of the means resolution lithography for the manufacture of SAW resonators : application to sources

Salut, Roland 15 November 2011 (has links)
Le but de ce travail de thèse est d’étudier les moyens de lithographie haute résolution pour la fabrication de résonateurs à ondes élastiques de surface, et de l’illustrer à travers la réalisation de sources de fréquences fonctionnant au-delà du GigaHertz. Dans un premier temps nous abordons les différents dispositifs fondés sur les ondes élastiques de surface puis les sources de fréquence (instabilités caractéristiques) et fixons les objectifs de l’étude au travers notamment d’un état de l’art. Dans un second temps, nous présentons les moyens de lithographie étudiés dans le cadre de ce travail, à savoir la lithographie électronique, la gravure par faisceau d’ions focalisés, la lithographie UV par projection et la lithographie par nano-impression. Pour chacune d’entre elles, nous détaillons le principe de fonctionnement et montrons, notamment grâce à des simulations, leur intérêt et leurs limitations. Ensuite, nous présentons la fabrication et la caractérisation de résonateurs sur différents types de substrats ayant des propriétés innovantes par rapport à nos applications. Le PZT élaboré par épitaxie, présentant des coefficients de couplage élevés (plusieurs pourcents) couplés à une granulométrie fine et une orientation cristalline selon l’axe 001. Le diamant, qui permet d’atteindre des vitesses de phase de l’ordre de 10000 m.s-1, soit une vitesse deux fois supérieure à celles des ondes transverses sur substrat de quartz, quartz que nous avons également étudié afin de rechercher de nouveaux points de fonctionnement à haute fréquence. Pour chaque matériau, nous identifions un ou plusieurs moyen(s) de lithographie qui nous permettent de fabriquer les résonateurs. Les étapes de conception, de fabrication et de caractérisation sont décrites en détail. La dernière partie du manuscrit consiste à exposer les caractéristiques des oscillateurs fondés sur les résonateurs à haut produit Qf ainsi fabriqués (Qf > 5.1012). Nous reportons les résultats obtenus à des fréquences de 1,5 GHz (sur quartz) et à 3 GHz (sur diamant nanocristallin). Le bruit de phase à 10 kHz de la porteuse est compris entre -100 et -110 dBc.Hz-1, et le bruit plancher est de -160 dBc.Hz-1. Nous concluons en donnant des pistes afin d’améliorer ces caractéristiques / The purpose of this thesis is to study high-resolution lithography for the fabrication of surface acoustic wave resonators, and to illustrate this technology through the realization of frequency sources operating beyond the Gigahertz. At first, we detail several devices based on surface acoustic waves and frequency sources (instability characteristics) and set the goals of the study in particular through a state of the art. In a second step, we present the lithography methods studied in this work : electron beam lithography, focused ion beam, UV lithography (stepper) and nano-imprint lithography. For each, we detail the operating principle and show, in particular through simulations, their interest and limitations. Then, we present the fabrication and characterization of resonators on different types of substrates with innovative properties compared to our applications. The epitaxial PZT exhibits high coupling coefficients (several percent) coupled with a fine particle size and crystal orientation along the axis 001. The diamond, which achieves phase velocities of about 10000 m.s-1, twice higher than those of STW waves on quartz substrate, quartz that we have also studied in order to search new operating points at high frequency. For each material, we identify one or more lithography methods that allow to manufacture the resonators. Design, fabrication and characterization steps are described in detail. The last part of the manuscript describes the characteristics of oscillators based on high Qf resonators (Qf > 5.1012). We report the results for operating frequencies of 1.5 GHz (on quartz) and 3 GHz (on nanocrystalline diamond). The phase noise at 10 kHz from the carrier is between -100 and -110 dBc.Hz-1, and the noise floor is -160 dBc.Hz-1. We conclude by giving ideas to improve these characteristics
223

Couplage AFM/Raman et spectroscopie Raman exaltée par effet de pointe de nanostructures / Study of nanostructures with AFM/Raman coupling device and Tip Enhanced Raman Spectroscopy (TERS)

Najjar, Samar 23 September 2013 (has links)
Pour mieux comprendre leurs propriétés, diverses nanostructures individuelles ont été étudiées à l’aide d’une technique couplant microscopie à force atomique et spectroscopie Raman confocale. Sous excitation lumineuse polarisée, la composition chimique, la structure et la présence de défauts a pu être précisée dans des nanobâtonnets d’oxydes métalliques (ZnO et α-Fe2O3). Sous irradiation laser résonnante, les spectres de nanotubes de carbone monoparoi enrobés de polymères ont révélé notamment l’absence de transfert de charge polymère-nanotube et un effet de désolvatation. Finalement, des feuillets de graphène oxydé et des ADNs double-brin peignés ont pu être préparés et caractérisés par spectroscopie Raman exaltée par effet de pointe en atteignant une résolution spatiale latérale voisine du rayon de courbure de l’apex de la pointe utilisée (12 nm), bien plus faible que la limite de diffraction, ce qui ouvre la voie à de nouveaux travaux spectroscopiques à l’échelle nanométrique. / To better understand their properties, various nanostructures have been studied using a technique combining atomic force microscopy and confocal Raman spectroscopy. Under polarized light excitation, the chemical composition, the structure and the presence of defects has been described in metal oxides nanorods (ZnO et α-Fe2O3). Under resonant laser excitation, Raman spectra of polymer-wrapped single-walled carbon nanotubes have revealed the absence of polymer-nanotube charge transfer and an effect due to desolvation. Finally, graphene oxide sheets and combed double-stranded DNAs have been prepared and characterized using tip-enhanced Raman spectroscopy with a lateral spatial resolution down to the curvature radius of the apex of the used tip (12 nm), well below the diffraction limit, which opens new opportunities for spectroscopic works at the nanometer scale.
224

Development of ozone and ammonia gas sensors on flexible substrate / Développement de capteurs d'ozone et d'ammoniac sur support souple

Acuautla Meneses, Monica Isela 19 September 2014 (has links)
L'émergence des nouvelles applications dans le domaine de la micro et nanotechnologie requière de faibles coûts de fabrication et la caractérisation de dispositifs électroniques ayant des propriétés telles que la flexibilité, la portabilité, la légèreté, et des matériaux de faibles coûts. Les méthodes traditionnelles de fabrication impliquent de longues étapes de production, et des procédés de fabrication impliquant des étapes avec des produits chimiques. Le but de cette thèse est d'étudier la conception et la caractérisation de capteurs d'ammoniac et d'ozone sur support souple fabriqués par des processus de photolithographie et de gravure laser. Le support flexible est composé de Kapton avec des électrodes interdigitées de Ti/Pt pour la détection de gaz et un microchauffage. Les motifs du circuit ont été réalisés par photolithographie et gravure laser. L'utilisation de gravure laser sur support souple permet de réduire les coûts liés au temps de fabrication, aussi représente une excellente alternative aux processus chimiques. Des nanoparticles de ZnO déposées par gouttes ont été utilisées comme matériaux sensibles en raison de leurs excellentes propriétés dans la détection de gaz. Les conditions de détection de gaz ont été étudiées pour différentes concentrations d'ozone et d'ammoniac. Afin de tester une méthode de dépôt utilisée dans la production industrielle à grande échelle, un dépôt par spray ultrasonique a été effectué. Les capteurs réalisés montrent une large gamme de détection de 5 ppb à 500 ppb à 200 °C pour l'ozone et de 5 ppm à 100 ppm à 300 °C pour l'ammoniac avec une bonne reproductibilité, stabilité et de rapides temps de réponse et de retourn. / Nowadays the emerging of new applications in the micro and nanotechnology field required to reduce fabrication costand to improve electronic devices with properties such as flexibility, portability, lightweight, and low cost. Traditional methods involve expensive and long production steps, and chemical vapor deposition. The purpose of this work is to present the conception and characterization of flexible ammonia and ozone sensors fabricated by photolithography and laser ablation processes. The flexible platform is composed of Kapton substrate with interdigitated Ti/Pt electrodes for gas detection and a micro-heater device. The circuit patterns were realized by photolithography and laser ablation. Photolithography is a well-known and reliable patterning process used on rigid substrate. The application of laser ablation process not only reduces fabrication time, but also represents an excellent viable alternative instead of chemical processes. ZnO thin films deposited by drop coating have been used as sensitive materials due to their excellent properties in the gas detection. The gas sensing condition and the performances of the devices are investigated for ozone and ammonia at different gas concentrations and different thin film thicknesses. In order to test a deposit methodology used in large scale industrial production, an ultrasonic spray deposition was done. The sensor provides a wide range of detection from 5 ppb to 500 ppb for ozone and from 5 ppm to 100 ppm for ammonia. Their best sensibilities were obtained at 200°C for ozone and 300 °C for ammoniac with good repeatability, stability and fast response/recovery time.
225

Élaboration et caractérisation de matériaux hybrides "nanoparticules Zn0 - cristaux liquides" pour applications aux cellules photovoltaïques / Elaboration and characterization of hybrid materials "nanoparticles ZnO - Liquid crystals" for photovoltaic cells applications

Halaby Macary, Mikhael 09 January 2019 (has links)
Ce travail de thèse s'inscrit dans l'essor important que connaît actuellement le domaine des énergies renouvelables en terme de recherche et de nouvelles technologies de l'énergie. Il est consacré à l'étude de nouveaux matériaux hybrides "nanoparticules ZnO - cristaux liquides" en vue d'applications aux cellules solaires de type hétérojonctions en volume. La motivation est d'utiliser les propriétés d'auto-organisation et de transport de charges des cristaux liquides et d'augmenter les interfaces donneur-accepteur afin d'améliorer leurs performances. Pour la mesures des mobilités des porteurs de charge, un banc de mesure "temps de vol" entièrement automatisé a été développé. Deux cristaux liquides calamitiques ont été caractérisés (DSC, microscopie optique polarisée, UV et "temps de vol"). Deux types de transports de charge, l'un ionique, l'autre électronique sont mis en évidence pour des charges positives et négatives avec des mobilités indépendantes du champ électrique et des comportements différents en fonction de la température. Un procédé d'élaboration des matériaux hybrides a été mis au point. Les caractérisations de ces matériaux montrent l'influence de la concentration en nanoparticules (0,05 à 38% en volume). La taille des domaines dans les phases cristal liquide augmente avec la concentration alors que la température de transition isotrope-SmA diminue fortement. Un résultat important est que les phénomènes de transport sont conservés pour des concentrations importantes (jusque 12% en volume). Le transport électronique est même amélioré. Les propriétés des matériaux élaborés apparaissent intéressantes pour des applications aux cellules photovoltaïques. / This thesis work is a part of the significant growth that is currently taking place in the field of the renewable energy in terms of research and new energy technologies. It is dedicated to the study of new hybrid material "zno particles - liquid crystals" for the applications in "bulk heterojunction" solar cells. The motivation is to increase the donor-acceptor interfaces in hybrid material and to combine the self-organizing and charge transport properties of liquid crystals, in order to improve their performance. A completely automated "time of flight" measuring set-up is developed, for the measurement of the charge carriers mobility in the aforementioned hybrid material. Using the dsc, polarized optical microscopy, uv-visible spectroscopy and "time of flight", we have characterized two calamitic liquid crystals. Two types of charge transport, one ionic, and the other electronic, are highlighted for positive and negative charges with electric field independent mobility and different behaviors with temperature. A process for the elaboration of hybrid materials is developed. The characterization of these materials show the influence of nanoparticles concentrations (0,05 to 38% by volume). The size of the domains in the liquid crystal phases increases with the concentration whereas the isotropic-sma phase transition temperature decreases monotically. Under controlled dispersion of zno nanoparticles in host liquid crystal up to 12% by volume, we have conserved the transport phenomena in hybrid material and study has shown that electronic transport is improved. The characterized hybrid materials have shown their potential application in organic photovoltaic.
226

Spectroscopie optique de l'oxyde de zinc / Zinc oxide optical spectroscpy

Marotel, Pascal 10 June 2011 (has links)
Ce travail porte sur l'étude des propriétés optiques de l'oxyde de zinc (ZnO), matériau semi-conducteur à grand gap. La technique de caractérisation principale de ce travail est la spectroscopie par photoluminescence, technique non destructive permettant d'obtenir des informations relatives à la structure électronique d'un matériau. Après avoir présenté les propriétés du ZnO, de ses alliages, et rappelé quelques principes de base associés à la luminescence des matériaux semi-conducteurs., nous comparerons dans un premier temps les propriétés optiques de différents types de ZnO monocristallin, selon leur mode d'élaboration : matériaux massifs de différentes origines, couches épitaxiées et nanofils. Ces comparaisons ainsi que l'étude des effets sur les spectres de photoluminescence des traitements tels que recuit et passivation nous permettront d'avancer différentes hypothèses quant à l'origine de la luminescence visible dans ce matériau grand gap, sujet encore controversé dans la littérature. Dans un deuxième temps, nous présenterons notre contribution à l'étude du dopage p du matériau, qui est encore aujourd'hui le verrou pour l'obtention de diodes électroluminescentes à base de ZnO. Nous examinerons le problème du dopage intrinsèque de type n et de la compensation, préalable indispensable avant d'aborder le dopage de type p. Le dopage p est traité ici principalement au travers des études optiques d'échantillons implantés et recuits. Plusieurs variantes liées à l'implantation d'azote seront présentées et l'obtention de paires donneur accepteurs clairement mise en évidence pour des conditions de recuit optimisées. La nature des accepteurs présents est discutée par référence aux travaux antérieurs. . / We have studied the optical properties of Zinc Oxide (ZnO), a wide band gap semiconductor material. The main characterization technique used in this work is the photoluminescence spectroscopy, a non destructive technique which gives information about the electronic structure of the material. After presenting the properties of ZnO, its alloys, and reminding some basic principles relative to the luminescence in semiconductor materials, we will compare the optical properties of ZnO single-crystals from different growth methods: bulk material from different origins, epitaxial layers and nanowires. These comparisons and the effects of different treatments (annealing, passivation...) on the PL spectra unable us to emit hypothesis about the origin of the visible luminescence, which is a controversial subject in the literature. Secondly, we will present our contribution to the study of the p doping of ZnO, which is indispensable for device applications based on the p–n junction. We will take a look at the n type intrinsic doping problem before examining the p type doping. We investigate here p type doping through optical studies of implanted and annealed samples. We present here some variants of nitrogen implantation and the presence of donor acceptor pairs has been proven, leading to the optimization of the annealing conditions. Nature of the acceptors is discussed with the literature.
227

ZnO micro- and nanostructures from Deep-UV photosensitive solutions for electronic and magnetic applications / Micro et nanostructures ZnO préparées par photolithographie UV profond pour des applications électroniques et magnétiques

Yeh, Chun-Cheng 07 November 2017 (has links)
Ce travail a consisté à mettre au point et étudier des formulations à base d’un précurseur photosensible de Zn (Zinc méthacrylate, ZnMAA). Déposé sous forme de film mince, ce précurseur peut être réticulé par une irradiation dans l’UV profond (193 nm). Il est montré que la réticulation est la conséquence d’une décomposition photoinduite partielle des précurseurs, qui provoque des réactions de condensations, conduisant à la formation du réseau Zn-O-Zn. Cette réaction a été caractérisée par spectroscopie FTIR, XPS et ellipsométrie (chapitre III). Il est montré qu’elle est partielle mais efficace pour conférer au matériau un caractère de résine à tonalité négative, pouvant être utilisée en écriture laser directe. Des structures submicrométriques ont été préparées avec cette résine. Les différentes étapes du procédé de photolithographie sont discutées dans le chapitre IV. En particulier, l’étape de recuit thermique pour obtenir un matériau ZnO est étudiée pour expliquer son impact sur la géométrie des structures obtenues. Le matériau ZnO structuré par cette voie est utilisé enfin pour fabriquer des dispositifs : transistor, capteur de gaz, réseau à propriétés magnétiques, prouvant l’intérêt de cette approche de microstructuration basée sur un matériau préparé par voie liquide. / In this thesis, an in-depth investigation to the photosensitive zinc methacrylate (ZnMAA) precursor was made. Zinc methacrylate can be crosslinked under DUV (193 nm) irradiation. The photo-induced solidification is attributed to the partial decomposition of the ZnMAA complex, which gives rise to the following hydrolysis-condensation reactions and the formation of Zn-O-Zn networks. The bonding variation and decomposition of organic species caused by DUV irradiation were carefully investigated by FTIR, XPS and ellipsometry and discussed in Chapter III. DUV irradiation provokes clivage of MAA ligands from zinc cations. However, the intensity of MAA ligands can only be reduced to ~2/3 of its initial intensity regardless the extension of irradiation time, implying only a small amount oxide network can be induced by DUV irradiation. The small amount of Zn-O-Zn networks inside the photo-irradiated regions can effectively decrease the solubility of photo-irradiated regions in polar solvents, which makes ZnMAA precursor just like a negative tone resist and able to be patterned into two-dimensional structures by DUV lithography. Due to good photosensitivity to DUV light (193 nm), the dimension of DUV-patterned ZnMAA structures can be decreased to sub-micro by using binary masks and the effects of each pattering step including (i) DUV exposure, (ii) prebaking and (iii) development on the size and shape of DUV-patterned ZnMAA structures are discussed in Chapter IV. In order to fabricate nanoscale ZnMAA structures, a home-made DUV interference system was used to pattern ZnMAA precursor and 300 nm periodic lines were successfully made. Applications as TFT transistor, gaz sensor and magnetic materials are shown.
228

Fabricação de microestruturas dopadas com nanofios de ZnO via fotopolimerização por absorção de dois fótons / Fabrication of microstructures doped with ZnO nanowires by two-photon absorption polymerization

Rodriguez, Ruben Dario Fonseca 24 July 2012 (has links)
No presente trabalho produzimos microestruturas, através da técnica de fotopolimerização via absorção de dois fótons, dopadas com nanofios de ZnO, um material que vem sendo amplamente explorado devido as suas interessantes propriedades ópticas e elétricas. Para a fabricação das microestruturas, utilizamos um oscilador laser de Ti:safira que produz pulsos de aproximadamente 100 fs em 800 nm. A intensidade dos pulsos de femtossegundos é alta o suficiente para induzir a absorção¬ de dois fótons em torno do volume focal, localizando a polimerização a esta região. Portanto, através da varredura do feixe na resina polimérica fabrica-se a estrutura desejada. Neste trabalho, desenvolvemos uma metodologia para introduzir nanofios de ZnO às microestruturas fabricadas, a partir da mistura do pó de nanofios de ZnO à resina acrílica. A resina utilizada é uma combinação de duas resinas, o etoxilated(6)trimethylolpropane triacrylate (SR-499) e tris(2-hydroxy ethyl)isocyanurate triacrylate (SR-368). Como fotoiniciador utilizamos o Lucirin TPO-L (2,4,6-trimetilbenzoiletoxifenil phosphine oxide). As microestruturas produzidas foram caracterizadas pelas técnicas de microscopia óptica, microscopia eletrônica de varredura, espectroscopia de energia dispersiva, difração de Raios X e espectroscopia de espalhamento micro-Raman. Através destas técnicas, foi possível observar a presença dos nanofios nas microestruturas, bem como caracterizar suas propriedades morfológicas que se mostram adequadas para o desenvolvimento de microdispositivos. Observamos também a emissão de fluorescência das microestruturas excitadas por um e dois fótons. Sendo assim, a metodologia de fabricação descrita aqui pode ser usada como mais uma opção na concepção de novos dispositivos tecnológicos. / In this study we fabricated microstructures, using the two-photon polymerization technique, containing ZnO nanowires, a material that has been widely exploited due to their interesting optical and electrical properties. For the microstructures fabrication, we used Ti:Sapphire laser oscillator operating at 800 nm with 100 fs pulses. The intensity of the fs-pulses is high enough to induce two-photon absorption, confining the excitation and thus the polymerization to the focal volume. By scanning the beam across the resin the desired microstructure is fabricated. In this work, we developed a method to introduce ZnO nanowires in the fabricated microstructure by mixing the ZnO nanowires powder to the acrylic resin. The used resin is a combination of two compounds, etoxilated(6)trimethylolpropane triacrylate (SR-499) and tris(2-hydroxy ethyl)isocyanurate triacrylate (SR-368). As a photoinitiator we have used Lucirin TPO-L (2,4,6-trimetilbenzoiletoxifenil phosphine oxide).The produced samples were characterized by optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction spectroscopy and micro-Raman scattering. From these techniques it was possible to observe the presence of nanowires in the microstructures, as well as to characterize the morphological properties, which has been shown to be interesting for developing microdevices. We have also observed fluorescent emission of the microstructures excites by one and two-photons absorption. Therefore, the methodology described here can be used as an alternative in the design of new optical devices.
229

Estudo de catalisadores de Ni/ZnO promovidos com CeO2 aplicados em reações de reforma a vapor do etanol e acetona / Study of Ni/ ZnO catalysts promoted with CeO2 applied in steam reforming reactions of ethanol and acetone

Elias, Kariny Ferreira Monteiro 27 April 2016 (has links)
A produção de energia é um dos grandes desafios deste século, principalmente com a necessidade no desenvolvimento de processos que utilizem preferencialmente fontes renováveis. Nesse contexto, é claro o interesse por pesquisas baseada no hidrogênio. Porém, os ganhos ambientais efetivos estão associados também à matéria-prima usada no processo de geração do hidrogênio, senso assim mais significativo quando do uso de fontes renováveis. No presente trabalho foi estudado o efeito da adição de diferentes teores de CeO2 em catalisadores de NiZnO, preparados pelo método da co-precipitação. Os catalisadores foram estudados frente à reação de reforma a vapor do etanol (RVE) para produção de H2, e no decorrer do trabalho foi pertinente incluir o estudo da reforma a vapor da acetona (RVA), como complemento dos estudos da RVE. Além disso, esta é uma molécula modelo para reforma a vapor do bio-óleo. Nos sistemas catalíticos sintetizados houve a formação da liga NiZn3, o que aparenta proporcionar um efeito sinérgico entre esses elementos. Observou-se um efeito altamente promotor do CeO2 com relação a diminuição do coque formado, devido a uma menor da formação da acetona, durante as etapas de reforma do etanol. O que consequentemente interferiu na produção de H2. O catalisador contendo 20% de CeO2 denominado NiZn20Ce apresentou um desempenho altamente promissor, pois de acordo com as análises de DRIFT, a presença do CeO2 levou a formação de espécies de formiato, o que consequentemente interferiu em uma menor formação de coque e maior produção de H2. Foi comprovado também que a natureza dos depósitos carbonáceos depende tanto do substrato utilizado quanto das etapas precursoras inicias que levarão a formação desse coque, sendo o ponto chave para um melhor desempenho do catalisador. / Energy production is one of the great challenges of this century, especially with the need to develop processes that use preferentially renewable sources. In this context, it´s evident the interest in research based on hydrogen. However, the environmental benefits are also associated with the raw material used on the hydrogen generation process, being more significant when used renewable sources. In the present work, it was studied the effect of CeO2 addition in NiZnO catalysts, prepared by coprecipitation method. The catalysts were studied front of the ethanol steam reforming reaction (ESR) to produce H2, and in the course of this study was relevant include study of acetone steam reforming (ASR), as a complement of ESR studies. Moreover, acetone is a molecule model for steam reforming of bio-oil. In the catalyst systems there has been the NiZn3 alloy formation, which provides a synergistic effect between these elements. It was observed a high CeO2 promoter effect regarding reduction of the formed coke, due to lower formation of acetone in the ethanol reforming steps, and consequently interfere in the H2 production. The catalyst denominated NiZn20Ce showed a high performance, according to DRIFT analyzes, the presence of the CeO2 led to the formation of species formate, which in turn interfere through a lower coke formation and higher H2 production. It was also established that the nature of the carbonaceous deposits depends as the substrate used as the precursors initial steps that led the formation of this coke, and it is the key to a better performance of the catalyst.
230

Estudo da fotocatálise heterogênea utilizando luz solar e ZnO como pré-tratamento de percolado de aterro sanitário / Study of application of ZnO using solar photoirradiation as pre-treatment of landfill leachate

Souza, Bruno Leandro Cortez de 31 October 2014 (has links)
O grande impacto ambiental causado pelo chorume proveniente de aterros sanitários impulsiona as pesquisas para o seu tratamento, com o objetivo de se obter a máxima degradação possível dos seus contaminantes recalcitrantes e tóxicos, diminuindo-se assim a sua toxicidade. O desenvolvimento de uma tecnologia eficiente e econômica para o tratamento é indispensável devido ao grande volume gerado e à legislação ambiental cada vez mais restritiva. Desta forma, os Processos Oxidativos Avançados (POAs) são avaliados como uma estratégia para o pré-tratamento, com um alto poder de degradação não seletivo e relação custo-benefício vantajosa. Dos diversos tipos de POAs existentes, aqueles que utilizam semicondutores para a fotocatálise heterogênea e luz solar como fonte de irradiação são os de maior interesse, devido a sua relativa eficiência, estabilidade fotoquímica, natureza não tóxica e baixo custo. Este estudo consistiu em avaliar o nível de degradação do chorume proveniente do aterro sanitário de Cachoeira Paulista - SP, utilizando como catalisador o ZnO irradiado pela luz solar, que possui um vasto espectro de fotoativação aliado ao seu baixo custo. As variáveis de entrada em dois níveis, foram o pH, o tempo de reação, a espessura da camada de ZnO impregnada sobre uma placa metálica e a concentração do efluente. Como variável resposta os valores de concentração expressa em Carbono Orgânico Total (COT) foi a mais adequada. O planejamento de experimentos utilizado foi o fatorial 23 com duplicata no ponto central. Na etapa delineatória, reduções de 28 % de COT foram alcançadas. A utilização da fotocatálise heterogênea utilizando ZnO fotoirradiado com luz solar se mostrou promissora para ser utilizada como um pré-tratamento do chorume. / The major environmental impact of leachate from landfills drives research to treat it, and aims to obtain the maximum degradation of their recalcitrant and toxic contaminants. The development of an efficient and economical treatment technology is indispensable due to the large volume generated and the increasingly restrictive environmental legislation. Thus, Advanced Oxidation Processes (AOPs) are evaluated as a strategy to pre-treatment with a high power non-selective degradation and advantageous cost-benefit ratio. From various types of POAs, those which use the heterogeneous photocatalytic semiconductor and solar light as the source of irradiation are the most interesting, because of its relative efficiency, photochemical stability, low cost and non-toxic nature. This study have assessed the level of degradation of the leachate from the landfill of Cachoeira Paulista - SP, using ZnO irradiated by sunlight as catalyst, which has a wide spectrum of photoactivation combined with its low cost. The input variables on two levels, were pH, reaction time, the thickness of the ZnO layer impregnated on a metal plate and concentration of the effluent. The most appropriate output variable was concentration, expressed in means of Total Organic Carbon (TOC). For the photocatalytic process, a factorial design (23) was used for the design of experiments. In final stage, reductions of 28% TOC were achieved. The use of heterogeneous photocatalysis using solar photoirradiated ZnO seems to be a great alternative as a pre-treatment of leachate.

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