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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.
71

Etude des processus pédogénétiques de technosols miniers : De l'analogue naturel à la stratégie de remédiation / Study of mine technosol pedogenic process : from natural analogous to the remediation strategy

Pascaud, Gregoire 12 October 2015 (has links)
Les Technosols comprennent les sols soumis à une forte pression anthropique et en particulier les sols influencés par les matériaux d'origine humaine. Dans ce contexte, les sites miniers abandonnés peuvent souvent contenir une grande quantité de déchets transformés enrichis en métaux et métalloïdes. En comparaison avec les sols naturels, la singularité des Technosols miniers correspond à leur matériel parental constitués de déchets minéraux de granulométrie fine. Contrairement à leurs homologues peu anthropisés, les Technosols sont encore assez mal connus. L'objectif global de cette étude est d'approfondir les connaissances des processus pédogénétiques des Technosols développés naturellement à partir de déchets miniers de façon à mieux anticiper la réhabilitation de ces sites. Ainsi, différents profils ont été échantillonnés correspondant respectivement à d’anciennes exploitations de W, Pb-Ag, Sn et Au. Leurs fonctionnements pédologiques ont dès lors été étudiés afin de déterminer les liens potentiels et les leviers guidant leur évolution. Cette étude préliminaire correspond à une image contemporaine de ce que peut donner une réhabilitation naturelle (par simple formation de solum après végétation spontanée) pour une durée d’environ 75 ans en moyenne. Dans un second temps plusieurs techniques de réhabilitation ont été étudiés respectivement: (i) la phytoremédiation par culture du Douglas ainsi que (ii) la revalorisation des déchets par synthèse de géopolymères enrichis en déchets miniers. / The Technosols include soils subject to strong anthropogenic pressure and particularly to the soil influenced by human-made materials. In this context, abandoned mine sites can contain a large amount of transformed waste materials often enriched with metals and metalloïds. Compared to natural soils, the singularity of mining Technosols naturally developed from mining waste corresponding to their parental material made by fine-grained mineral waste. Unlike their poorly anthropized homologous, Technosols are not enough well known. So, the overall objective of this study is to increase knowledge of soil processes of Technosols after spontaneous vegetation impact. Thus, different profiles were sampled respectively corresponding to different abandoned mine exploitation type: W, Pb-Ag, Sn and Au. Their pedogenic way have therefore been studied to determine potential linkages and levers guiding their evolution. This preliminary study is based on the contemporary picture of a natural rehabilitation (by simple solum formation) for a period of about 75 years on average. Secondly several rehabilitation techniques have been studied respectively: (i) the phytoremediation by growing Douglas plant and (ii) the reused of waste by mine sediment based geopolymer synthesis.
72

Vertical Organic Field-Effect Transistors: On the understanding of a novel device concept

Günther, Alrun Aline 15 July 2016 (has links)
Diese Arbeit stellt eine eingehende Studie des sogenannten Vertikalen Organischen Feld-Effekt-Transistors (VOFET) dar, einer neuen Transistor-Geometrie, welche dem stetig wachsenden Bereich der organischen Elektronik entspringt. Dieses neuartige Bauteil hat bereits bewiesen, dass es in der Lage ist, eine der fundamentalen Einschränkungen herkömmlicher organischer Feld-Effekt-Transistoren (OFETs) zu überwinden: Die für Schaltfrequenz und An-Strom wichtige Kanallänge des Transistors kann im VOFET stark reduziert werden, ohne dass teure und komplexe Strukturierungsmethoden genutzt werden müssen. Das genaue Funktionsprinzip des VOFET ist bisher jedoch weitgehend unerforscht. Durch den Vergleich von experimentellen Daten mit Simulationsdaten des erwarteten Bauteil-Verhaltens wird hier ein erstes, grundlegendes Verständnis des VOFETs erarbeitet. Die so gewonnenen Erkenntnisse werden im Folgenden genutzt, um bestimmte Parameter des VOFETs kontrolliert zu manipulieren. So wird beispielsweise gezeigt, dass die Morphologie des organischen Halbleiters, und damit seine Abscheidungsparameter, sowohl für die VOFET-Herstellung als auch für den Ladungsträgertransport im fertigen Bauteil eine wichtige Rolle spielen. Weiterhin wird gezeigt, dass der VOFET, genau wie der konventionelle OFET, durch das Einbringen von Kontaktdotierung deutlich verbessert werden kann. Mit Hilfe dieser Ergebnisse kann gezeigt werden, dass das Funktionsprinzip des VOFETs mit dem eines konventionellen OFETs nahezu identisch ist, wenn man von geringen Abweichungen aufgrund der unterschiedlichen Geometrien absieht. Basierend auf dieser Erkenntnis wird schließlich ein VOFET präsentiert, welcher im Inversionsmodus betrieben werden kann und so die Lücke zur konventionellen MOSFET-Technologie schließt. Dieser Inversions-VOFET stellt folglich einen vielversprechenden Ansatz für leistungsfähige organische Transistoren dar, welche als Grundbausteine für komplexe Elektronikanwendungen auf flexiblen Substraten genutzt werden können.:Zusammenfassung 5 Abstract 6 Publications 13 Introduction 17 Basic Principles of Organic Semiconductors and Related Devices 23 1. The Physics of Organic Semiconductors 25 1.1. Electronic and structural properties of organic semiconductors 28 1.2. Charge carrier transport 34 1.3. Doping of organic semiconductors 43 2. Organic field-effect transistors 47 2.1. Operational principle 50 2.2. Functional interfaces in OFETs 55 2.3. Contact resistance and short-channel effects in OFETs 60 2.4. Applications of OFETs and related devices 65 3. Vertical organic transistors 77 3.1. Organic permeable-base transistors (OPBTs) and organic static induction transistors (OSITs) 81 3.2. Organic Schottky barrier transistors (OSBTs) 85 3.3. Vertical organic field-effect transistors (VOFETs) 90 Study of the Vertical Organic Field-Effect Transistor 97 4. Methods and Materials 99 4.1. Materials 101 4.2. Sample preparation 104 4.3. Sample characterisation 110 5. Material Optimisation for VOFETs 121 5.1. Variation of the source insulator 123 5.2. Effects of the pentacene morphology 133 5.3. Summary 137 6. Charge Transport in the VOFET 139 6.1. Simulating current flow in the VOFET 141 6.2. The vertical channel 154 6.3. Charge transport in pentacene 161 6.4. Effects of mobility and layer thickness in pentacene VOFETs 167 6.5. Summary 175 7. Doping Concepts for VOFETs 177 7.1. Doping of the bulk regions 179 7.2. Selective contact doping 183 7.3.Impact on the understanding of VOFET operation 194 7.4. Summary 198 8. Vertical Organic Inversion Transistors 201 8.1. Discussion of suitable material systems 204 8.2. Realising inversion VOFETs 207 8.3. Summary 212 9. Conclusion and Outlook 215 9.1. Conclusion 217 9.2. Outlook 219 Appendix 221 A. XRD spectra of pentacene films 223 B. Additional simulation data 227 Bibliography 229 Addresses 257 Important Symbols, Constants and Abbreviations 263 List of Figures 271 Acknowledgements 283 / This work represents a comprehensive study of the so-called vertical organic field-effect transistor (VOFET), a novel transistor geometry originating from the fast-growing field of organic electronics. This device has already demonstrated its potential to overcome one of the fundamental limitations met in conventional organic transistor architectures (OFETs): In the VOFET, it is possible to reduce the channel length and thus increase On-state current and switching frequency without using expensive and complex structuring methods. Yet the VOFET's operational principles are presently not understood in full detail. By simulating the expected device behaviour and correlating it with experimental findings, a basic understanding of the charge transport in VOFETs is established and this knowledge is subsequently applied in order to manipulate certain parameters and materials in the VOFET. In particular, it is found that the morphology, and thus the deposition parameters, of the organic semiconductor play an important role, both for a successful VOFET fabrication and for the charge transport in the finished device. Furthermore, it is shown that VOFETs, just like their conventional counterparts, are greatly improved by the application of contact doping. This result, in turn, is used to demonstrate that the VOFET essentially works in almost exactly the same way as a conventional OFET, with only minor changes due to the altered contact arrangement. Working from this realisation, a vertical organic transistor is developed which operates in the inversion regime, thus closing the gap to conventional MOSFET technology and providing a truly promising candidate for high-performance organic transistors as the building blocks for advanced, flexible electronics applications.:Zusammenfassung 5 Abstract 6 Publications 13 Introduction 17 Basic Principles of Organic Semiconductors and Related Devices 23 1. The Physics of Organic Semiconductors 25 1.1. Electronic and structural properties of organic semiconductors 28 1.2. Charge carrier transport 34 1.3. Doping of organic semiconductors 43 2. Organic field-effect transistors 47 2.1. Operational principle 50 2.2. Functional interfaces in OFETs 55 2.3. Contact resistance and short-channel effects in OFETs 60 2.4. Applications of OFETs and related devices 65 3. Vertical organic transistors 77 3.1. Organic permeable-base transistors (OPBTs) and organic static induction transistors (OSITs) 81 3.2. Organic Schottky barrier transistors (OSBTs) 85 3.3. Vertical organic field-effect transistors (VOFETs) 90 Study of the Vertical Organic Field-Effect Transistor 97 4. Methods and Materials 99 4.1. Materials 101 4.2. Sample preparation 104 4.3. Sample characterisation 110 5. Material Optimisation for VOFETs 121 5.1. Variation of the source insulator 123 5.2. Effects of the pentacene morphology 133 5.3. Summary 137 6. Charge Transport in the VOFET 139 6.1. Simulating current flow in the VOFET 141 6.2. The vertical channel 154 6.3. Charge transport in pentacene 161 6.4. Effects of mobility and layer thickness in pentacene VOFETs 167 6.5. Summary 175 7. Doping Concepts for VOFETs 177 7.1. Doping of the bulk regions 179 7.2. Selective contact doping 183 7.3.Impact on the understanding of VOFET operation 194 7.4. Summary 198 8. Vertical Organic Inversion Transistors 201 8.1. Discussion of suitable material systems 204 8.2. Realising inversion VOFETs 207 8.3. Summary 212 9. Conclusion and Outlook 215 9.1. Conclusion 217 9.2. Outlook 219 Appendix 221 A. XRD spectra of pentacene films 223 B. Additional simulation data 227 Bibliography 229 Addresses 257 Important Symbols, Constants and Abbreviations 263 List of Figures 271 Acknowledgements 283
73

Joint Project: Interaction and transport of actinides in natural clay rock with consideration of humic substances and clay organics - Characterization and quantification of the influence of clay organics on the interaction and diffusion of uranium and americium in the clay

Schmeide, Katja, Bernhard, Gert January 2012 (has links)
The objective of this project was the study of basic interaction processes in the systems actinide - clay organics - aquifer and actinide - natural clay - clay organics - aquifer. Thus, complexation, redox, sorption and diffusion studies were performed. To evaluate the influence of nitrogen, phosphorus and sulfur containing functional groups of humic acid (HA) on the complexation of actinides in comparison to carboxylic groups, the Am(III) and U(VI) complexation by model ligands was studied by UV-Vis spectroscopy and TRLFS. The results show that Am(III) is mainly coordinated via carboxylic groups, however, probably stabilized by nitrogen groups. The U(VI) complexation is dominated by carboxylic groups, whereas nitrogen and sulfur containing groups play a minor role. Phosphorus containing groups may contribute to the U(VI) complexation by HA, however, due to their low concentration in HA they play only a subordinate role compared to carboxylic groups. Applying synthetic HA with varying sulfur contents (0 to 6.9 wt.%), the role of sulfur functionalities of HA for the U(VI) complexation and Np(V) reduction was studied. The results have shown that sulfur functionalities can be involved in U(VI) humate complexation and act as redox-active sites in HA for the Np(V) reduction. However, due to the low content of sulfur in natural HA, its influence is less pronounced. In the presence of carbonate, the U(VI) complexation by HA was studied in the alkaline pH range by means of cryo-TRLFS (-120°C) and ATR FT-IR spectroscopy. The formation of the ternary UO2(CO3)2HA(II)4− complex was detected. The complex formation constant was determined with log β0.1 M = 24.57 ± 0.17. For aqueous U(VI) citrate and oxalate species, luminescence emission properties were determined by cryo-TRLFS and used to determine stability constants. The existing data base could be validated. The U(VI) complexation by lactate, studied in the temperature range 7 to 65°C, was found to be endothermic and entropy-driven. In contrast, the complex stability constants determined for U(VI) humate complexation at 20 and 40°C are comparable, however, decrease at 60°C. For aqueous U(IV) citrate, succinate, mandelate and glycolate species stability constants were determined. These ligands, especially citrate, increase solubility and mobility of U(IV) in solution due to complexation. The U(VI) sorption onto crushed Opalinus Clay (OPA, Mont Terri, Switzerland) was studied in the absence and presence of HA or low molecular weight organic acids, in dependence on temperature and CO2 presence using OPA pore water as background electrolyte. Distribution coefficients (Kd) were determined for the sorption of U(VI) and HA onto OPA with (0.0222 ± 0.0004) m3/kg and (0.129 ± 0.006) m3/kg, respectively. The U(VI) sorption is not influenced by HA (50 mg/L), however, decreased by low molecular weight organic acids (> 1×10-5 M), especially by citrate and tartrate. With increasing temperature, the U(VI) sorption increases both in the absence and in the presence of clay organics. The U(VI) diffusion in compacted OPA is not influenced by HA at 25 and 60°C. Predictions of the U(VI) diffusion show that an increase of the temperature to 60°C does not accelerate the migration of U(VI). With regard to uranium-containing waste, it is concluded that OPA is suitable as host rock for a future nuclear waste repository since OPA has a good retardation potential for U(VI).
74

The use of bimetallic heterogeneous oxide catalysts for the Fenton reaction

Mgedle, Nande January 2019 (has links)
M.Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology / Water contaminated with non-biodegradable organics is becoming increasing problematic as it has a hazardous effect on human health and the aquatic environment. Therefore, the removal of organic contaminants is of importance and an active heterogeneous Fenton catalyst is thus required. The literature indicates that a bimetallic oxide Fenton catalyst is more active than an iron oxide catalyst. This study focused on increasing the activity of iron-based Fenton catalysts with the addition of transition metals such as manganese, cobalt and copper and optimizing the preparation method. In this study, bimetallic oxide (Fe-Cu, Fe-Mn, Fe-Co) and monometallic oxide (Fe, Cu, Mn,Co) catalysts supported on silica SiO2 where prepared by incipient wetness impregnation. The total metal oxide contents were kept constant. The catalysts where calcined in two different ways, in a conventional oven and in a microwave. These catalysts were characterized with XRD, XPS and CV and were tested for the degradation of methylene blue dye at 27°C. The catalysts calcined in a microwave oven had a higher catalytic activity than those prepared in a conventional oven. The bimetallic oxide catalysts outperformed the mono- metallic oxide catalysts in the degradation of methylene blue. The Fe2MnOx prepared by microwave energy were the most active catalyst yielding the highest percentage of degradation of methylene blue dye (89.6%) after 60 minutes. The relative amounts of manganese and iron oxide were varied while keeping the total metal content in the catalyst the same. The optimum ratio of Fe to Mn was 1:7.5 since it yielded the most active catalyst. A 96.6 % removal of methylene blue was achieved after 1 hour of degradation. Lastly this ratio 1Fe:7.5Mn was prepared by varying different microwave power (600, 700 and 800 W) and irradiation time (10, 20 and 30 min). The optimum microwave power and irradiation time was 800W and 10 min with the methylene blue percentage removal of 96.6 % after 1 hour of degradation.
75

Spectral Study of Asteroids and Laboratory Simulation of Asteroid Organics

Hargrove, Kelsey 01 January 2015 (has links)
We investigate the spectra of asteroids at near- and mid-infrared wavelengths. In 2010 and 2011 we reported the detection of 3 ?m and 3.2-3.6 ?m signatures on (24) Themis and (65) Cybele indicative of water-ice and complex organics [1] [2] [3]. We further probed other primitive asteroids in the Cybele dynamical group and Themis family, finding diversity in the shape of their 3 ?m [4] [5] [6] and 10 ?m spectral features [4]. These differences indicated mineralogical and compositional variations within these asteroid populations. Also in the mid-infrared region we studied a larger population of asteroids belonging to the Bus C, D, and S taxanomic classes to understand the relationship between any mineralogy and hydration inferred in the visible and near- infrared with the shape, strength, and slope of the 10 ?m emission. We have discovered that at least 3 of the main Bus taxanomic groups (Cs, Ds, and Ss as defined by their visible spectra) clearly cluster into 3 statistically distinct groups based on their 8-13 ?m spectra. Additionally we have attempted to simulate in a laboratory the possible organic compounds we have detected on two asteroids, using various mixtures containing aromatic and aliphatic hydrocarbons. We find that asteroid (24) Themis and (65) Cybele have ?CH2/?CH3 and NCH2/NCH3 ratios similar to our 3- methylpentane, propane, and hexane residues, suggesting that the organics on these asteroids may be short chained and/or highly branched. The ?CH2/?CH3 and NCH2/NCH3 for asteroid(24)Themis are most consistent with the DISM, and some carbonaceous chondrites. The band centers of the C-H stretch absorptions indicate that both asteroids may have aliphatic carriers chemically bonded to electronegative groups (i.e. aromatics), and some that are not. We also detect a 3.45 ?m feature in the spectra of both asteroids that is present in several dense molecular clouds. Our results suggest an interstellar origin for the organics on (24) Themis, and likely (65) Cybele. The differences in the organics of Themis and Cybele are likely related to variations in thermal processing, irradiation and/or formation region in the solar nebula.
76

Direct Imaging of Plant Metabolites in the Rhizosphere Using Laser Desorption Ionization Ultra-High Resolution Mass Spectrometry

Lohse, Martin, Haag, Rebecca, Lippold, Eva, Vetterlein, Doris, Reemtsma, Thorsten, Lechtenfeld, Oliver J. 30 March 2023 (has links)
The interplay of rhizosphere components such as root exudates, microbes, and minerals results in small-scale gradients of organic molecules in the soil around roots. The current methods for the direct chemical imaging of plant metabolites in the rhizosphere often lack molecular information or require labeling with fluorescent tags or isotopes. Here, we present a novel workflow using laser desorption ionization (LDI) combined with mass spectrometric imaging (MSI) to directly analyze plant metabolites in a complex soil matrix. Undisturbed samples of the roots and the surrounding soil of Zea mays L. plants from either field- or laboratory-scale experiments were embedded and cryosectioned to 100 mm thin sections. The target metabolites were detected with a spatial resolution of 25 mm in the root and the surrounding soil based on accurate masses using ultra-high mass resolution laser desorption ionization Fourier-transform ion cyclotron resonance mass spectrometry (LDI-FT-ICR-MS). Using this workflow, we could determine the rhizosphere gradients of a dihexose (e.g., sucrose) and other plant metabolites (e.g., coumaric acid, vanillic acid). The molecular gradients for the dihexose showed a high abundance of this metabolite in the root and a strong depletion of the signal intensity within 150 mm from the root surface. Analyzing several sections from the same undisturbed soil sample allowed us to follow molecular gradients along the root axis. Benefiting from the ultra-high mass resolution, isotopologues of the dihexose could be readily resolved to enable the detection of stable isotope labels on the compound level. Overall, the direct molecular imaging via LDI-FT-ICR-MS allows for the first time a nontargeted or targeted analysis of plant metabolites in undisturbed soil samples, paving the way to study the turnover of root-derived organic carbon in the rhizosphere with high chemical and spatial resolution.
77

福爾摩莎的糧食民主: 台灣有機食品自耕農的問題與前景 / Food Democracy in Formosa: Problems and Prospects for Independent Farmers in Taiwan’s Organic Food Sector

辛介石, Peter Singer-Towns Unknown Date (has links)
研究目的主要是根據參與有機事業的觀點更進一步了解台灣有機領域的狀況。 訪問七位於北台灣的有機領域的參與者進行非正式訪談:有機農戶、店家、有機商品認證機構回答相關有機領域的問題和消費者問卷調查。研究結果顯示獨立有機農戶所面臨一些挑戰和台灣糧食民主機制下運作的潛力—獨立有機農戶處理大部分財團的競爭和有機標誌混淆消費者的狀況下。由於真正問題並非在食物的品質本身於是焦點可轉向對於有機農戶或其他獨立生產機構有利的狀況。最後,本研究將提供一些建議給未來的研究以及提供目前問題的可能解決方法。 / The purpose of this study is to further the understanding of the state of the organic food industry in Taiwan with special consideration given to the perspectives of those participating in it. Seven participants in the organic foods industry in Northern Taiwan were selected for informal interviews. Farmers, store owners, and an organic food certification authority answered questions about the organic food industry, and consumers were surveyed as well. The findings uncovered several challenges that independent organic farmers face, and that the rate of Food Democracy in Taiwan is operating below its potential, as independent farmers deal with competition from dominant corporations, while the organic labeling system confuses consumers. Since the problem is not with the quality of the food, focus can be shifted toward ensuring a level playing field for farmers with smaller independent operations. Finally, this study gives several suggestions for avenues of future research and offers possible solutions to the problems uncovered.
78

Cellules photovoltaïques organiques souples à grande surface

Bailly, Loïc 03 September 2010 (has links)
Afin d’obtenir une approche où l’aspect industriel du projet est soutenu par les connaissances académiques et les capacités analytiques du monde de la recherche, ce travail portant sur les cellules photovoltaïques organiques souples grande surface commence par décrire l’énergie photovoltaïque dans son ensemble. Les tenants et aboutissants de son développement sont détaillés, ainsi que ses filières technologiques. Les semi-conducteurs organiques, les mécanismes physiques mis en jeu dans la production d’électricité d’origine photovoltaïque et les grandeurs électriques associées aux cellules photovoltaïques organiques ainsi que les différentes structures de celles-ci sont ensuite présentés. Les dispositifs réalisés dans le cadre de ce travail sur les cellules photovoltaïques organiques sont présentés. Les différentes techniques de dépôt de couches minces, aussi bien celles permettant la production en masse que celles permettant la production à plus petite échelle sont présentées. Cette présentation s’accompagne d’une recherche qui se veut exhaustive des publications relatant l’utilisation des ces techniques d’impression afin de créer des dispositifs photovoltaïques organiques. Une comparaison de ces différentes techniques est menée afin de déterminer les modes de production pertinents. Une étude bibliographique complète menée sur les cellules « grande surface » est présentée. Les cellules et modules réalisés grâce au procédé pilote d’enduction par héliogravure sont ensuite présentés. Le travail réalisé sur un autre procédé, le « doctor blade », est ensuite exposé. Enfin, la problématique du séchage et du recuit des couches minces déposées en continu est posée, et le traitement micro-onde proposé comme solution. / To obtain an approach where the industrial aspect of the project is supported by academic knowledge and the analytical capacities of research, this work concerning the large area flexible organic solar cells begins by describing the photovoltaic energy in general. The ins and outs of its development are detailed, as well as the different technologies involved. The organic semiconductors, the physical mechanisms involved in the photovoltaic electricity production and the physical values attached to the organic solar cells as well as the various structures of these cells are then presented. Devices realized within the framework of this work are then presented. The various techniques of depositing thin layers allowing the mass production as well as those allowing the smaller-scale production are presented. This presentation comes along with an exhaustive research of the publications telling the use of these techniques of printing to create organic photovoltaic devices. A comparison of those various techniques is led to determine the relevant means of production. A complete bibliographical study led on large area organic solar cells is presented. Cells and modules realized thanks to the experimental process of heliogravure coating are then presented. The work realized with another process called doctor blade is then exposed. Finally, the problem of the drying and annealing of the thin layers deposited continuously is raised, and the microwave treatment proposed as a possible solution.
79

Μελέτη και ανάπτυξη φωτοευαίσθητων ηλεκτροδίων για την φωτοηλεκτροχημική διάσπαση του νερού

Σεφερλής, Ανδρέας 03 May 2010 (has links)
Το αντικείμενο της διδακτορικής διατριβής είναι η σύνθεση, ο χαρακτηρισμός και η μελέτη φωτοευαίσθητων ηλεκτροκαταλυτών TiO2 και η μορφοποίηση τους σε ηλεκτρόδια, τα οποία και μελετήθηκαν ως προς την φωτοηλεκτροχημική παραγωγή υδρογόνου από νερό ή/και οργανικές ενώσεις. Τα ηλεκτρόδια λεπτών υμενίων παρασκευάστηκαν με τη μέθοδο εμβάπτισης – επίστρωσης σε διάλυμα TiO2. Τα ηλεκτρόδια Τιτάνιας ήταν νανοπορώδη και παρουσίαζαν νανοκρυσταλλική δομή ανατάση με μέγεθος σωματιδίων 15 nm. Η μελέτη των ηλεκτροδίων πραγματοποιήθηκε σε φωτοηλεκτροχημικό αντιδραστήρα. Τα αποτελέσματα έδειξαν ότι η φωτοβόληση των ηλεκτροδίων τιτάνιας τα ενεργοποιεί, διεγείροντας ηλεκτρόνια στη ζώνη αγωγιμότητας και δημιουργώντας οπές στη ζώνη σθένους. Για την παραγωγή υδρογόνου ήταν απαραίτητη η επιβολή δυναμικού ή η παρουσία οργανικών ενώσεων στον ηλεκτρολύτη. Ο ρυθμός παραγωγής υδρογόνου βελτιστοποιήθηκε συναρτήσει του πάχους του υμενίου και της συγκέντρωσης των οργανικών ενώσεων στον ηλεκτρολύτη. Συμπερασματικά έχει τεράστιο δυναμικό για εφαρμογή σε φωτοηλεκτροχημικά κελιά καυσίμου για ταυτόχρονο καθαρισμό υδάτων από οργανικούς ρύπους και παραγωγή ενός «καθαρού» καυσίμου, του υδρογόνου. / The object of this thesis is the composition, characterization and the study of photosensitive TiO2 electrocatalysts and their formation in electrodes, which were studied for the photoelectrochemical production of hydrogen from water and/or organic compounds. The thin film electrodes were prepared with the dip - coating method in TiO2 solution. The titania electrodes were nanoporous and nanocrystaline, of anatase phase with particle size 15 nm. The study of electrodes took place in a photoelectrochemical reactor. The results showed that the illumination of the titania electrode activates it, arousing electrons in the conduction band and creating holes in the valence band. For the production of hydrogen, it was necessary to apply potential, or the presence of organic compounds in the electrolyte. The production rate of hydrogen was optimised with respect to the thickness of the film and the concentration of organic compounds in the electrolyte. In conclusion, this method has enormous potential for application in photoelectrochemical fuel cells for simultaneous cleaning of water from organic pollutants and production of “clean” fuel, hydrogen.
80

Crescimento e caracterização óptica de cristais de L-Asparagina pura e L-Asparagina irradiada

Fujita, Alessandra Keiko Lima 15 February 2012 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work we present the results of L-asparagine H2O crystal growth and the study of their optical properties, linear and nonlinear, of crystal as grown and after being submitted to high doses of X-ray. Crystals were grown in aqueous solution by the method of slow evaporation of the solvent. Measurements optical absorption, Raman, thermal analysis and efficiency of second harmonic generation were carried out. The results demonstrate the good optical quality of the crystals for use in optical devices, comparable to that of KDP (KH2PO4). . / Neste trabalho apresentamos os resultados do crescimento de cristais de L-Asparagina-H2O e do estudo de suas propriedades ópticas, lineares e não lineares, do cristal como é crescido e após ser submetido a altas doses de raios-X. Os cristais foram crescidos em solução aquosa pelo método de evaporação lenta do solvente. Foram realizadas medidas de absorção óptica, Raman, análise térmica e eficiências de geração de segundo harmônico. Os resultados demonstram as boas qualidades ópticas dos cristais para aplicação em dispositivos ópticos, comparáveis ao do KDP (KH2PO4).

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