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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.
41

Numerical Analysis of Multiphase Flow in Bubble Columns and Applications for Microbial Fuel Cells

Picardi, Robert N. 15 April 2015 (has links)
Computational fluid dynamics (CFD) modeling was used to predict the hydrodynamics of a column reactor. Bubble columns have applications across many engineering disciplines and improved modeling techniques help to increase the accuracy of numerical predictions. An Eulerian-Eulerian multi-fluid model was used to simulate fluidization and to capture the complex physics associated therewith. The commercial code ANSYS Fluent was used to study two-dimensional gas-liquid bubble columns. A comprehensive parameter study, including a detailed investigation of grid resolution was performed. Specific attention was paid to the bubble diameter, as it was shown to be related to cell size have significant effects on the characteristics of the flow. The parameters used to compare the two-dimensional (2D) cases to experimental results of Rampure, et. al. were then applied to a three-dimensional (3D) geometry. It was demonstrated that the increase in accuracy from 2D to 3D is negligible compared to the increase in CPU required to simulate the entire 3D domain. Additionally, the reaction chamber of a microbial fuel cell (MFC) was modeled and a preliminary parameter study investigating inlet velocity, temperature, and acetate concentration was conducted. MFCs are used in wastewater treatment and have the potential to treat water while simultaneously harvesting electricity. The spiral spacer and chemical reactions were modeled in a 3D geometry, and it was determined that inlet velocity was the most influential parameter that was simulated. There were also significant differences between the 2D and 3D geometries used to predict the MFC hydrodynamics. / Master of Science
42

Optimisation d'anodes microbiennes à partir de lixiviat de sol pour la conception de piles à combustible microbiennes / Optimisation of microbial anodes from soil leachate for designing microbial fuel cells

Pocaznoi, Diana 18 July 2012 (has links)
Les piles à combustible microbienne (PACMs) sont des piles capables de convertir l'énergie chimique de combustibles organiques directement en énergie électrique. Dans ces piles, l'oxydation du combustible est assurée par des micro-organismes dits "électro-actifs" qui forment des biofilms à la surface de l'anode et jouent le rôle de catalyseur des réactions électrochimiques. Les travaux qui font l'objet de ce manuscrit ont eu pour objectif d'optimiser des anodes microbiennes formées à partir de la flore bactérienne contenue dans des terreaux de jardin. Les expériences effectuées en chronoampérométrie avec un système à trois électrodes ont conduit à la première démonstration expérimentale que des densités de courant de 66 A/m2 pouvaient être obtenues en formant les anodes microbiennes sur des ultra-microélectrodes. Sur des électrodes de taille normale, la mise au point d'une nouvelle technique (polarisation retardée) pour la formation de biofilms microbiens a permis d'obtenir des densités de courant de 9,4 A/m2 après seulement 3 jours de polarisation tandis que le protocole conventionnel demandait quelques semaines pour obtenir 6 à 8 A/m2. L'étude de différents matériaux d'électrode a indiqué que l'acier inoxydable qui permit d'atteindre des densités de courant de 21 A/m2 présente un grand intérêt pour la formation de biofilms électro-actifs. En effet, les électrodes en tissu de carbone ont assuré jusqu'à 34,3 A/m2, voire 50 A/m2 en anaérobiose, mais elles bénéficiaient d'une structure tridimensionnelle. La mise en oeuvre des anodes microbiennes optimisées dans les PACMs a assuré la production de 6,0 W/m2. L'élaboration d'un nouveau prototype intégrant un système de cathode amovible a permis d'allonger la durée de vie initiale de la pile de 2 semaines à plus de 2 mois / Microbial fuel cells (MFC) are devices capable to convert chemical energy from organic fuels directly into electrical energy. In these cells, the fuel oxidation is provided by micro-organisms known as "electro-active"; these microorganism form biofilms on the surface of the anode and act as a catalyst for electrochemical reactions. The aim of this work was the optimisation of microbial anodes formed from bacterial flora contained in garden soils. The chronoamperometric experiments performed in a three-electrode system showed for the very first time in these systems that current densities of 66 A/m2 could be obtained by forming microbial anodes on ultra-microelectrodes. On electrode of normal size, the development of a new technique (delayed polarisation) for designing microbial biofilms produced current densities of 9.4 A/m2 after 3 days of polarisation, while the conventional protocol asked a few weeks for obtaining 6 to 8 A/m2. The study of different electrode materials indicated that stainless steel allowed reaching current densities up to 21 A/m2, which makes it a suitable candidate for designing electro-active biofilms. Indeed, the carbon electrodes provided up to 34.4 A/m2, even 50 A/m2 in anaerobic conditions, but the electrodes benefited of a three-dimensional structure contrasting the stainless steel electrode. The use of optimised microbial anodes in MFCs insured the production of 6 W/m2. In addition, the development of a new prototype containing a removable cathode allowed extending the lifetime of the initial MFC from 2 weeks to over 2 months
43

Performance analysis of bioanode materials and the study of the metabolic activity of Rhodopseudomonas palustris in photo-bioelectrochemical systems

Pankan, Aazraa Oumayyah January 2019 (has links)
A sustainable and low-cost system, namely a photo-bioelectrochemical system (photo-BES), based on the natural blueprint of photosynthetic microorganisms was studied. The aim of this research work is to improve the efficiency of electron transfer of the microorganisms for bioelectricity generation. The first strategy adopted was the evaluation of the exoelectrogenic activity of oxygenic photosynthetic cyanobaterium, Synechococcus elongatus PCC 7942, in biophotovoltaic (BPV) platforms through a comparative performance analysis of bioanode materials. The second approach involved improving the performance of anoxygenic photosynthetic bacterium, Rhodopseudomonas palustris ATCC® 17001™, by varying the ratio of nitrogen to carbon sources (N:C) to maximise both biohydrogen production and exoelectrogenesis for conversion into bioelectricity in photosynthetic microbial fuel cells (photoMFCs). A linear correlation was obtained between average surface roughness/surface area and maximum power density of ITO-coated and graphene/ITO-coated substrates. Graphene/ITO-coated PET bioanodes produced the highest maximum power output of 29±4 μW m-2 in a single chamber BPV device due to improved biofilm formation and improved electrochemical activity. XG Leaf®, also known as graphene paper, helped to bridge the shortcomings of carbon fibres in terms of wettability. The most hydrophilic, 240 μm thick graphene paper, produced the highest maximum power output of 393±20 μW m-2 in a membrane electrode assembly (MEA)-type BPV device, mainly due to reduced electrochemical polarisation. A proof of concept study compared the performance of screen-printed graphene onto a membrane separator against 3D-printed bioanodes coated with carbon nanotubes. One mm thick 3D-printed bioanode was better performing as its structures promoted a much denser biofilm with extensive fibrous extracellular matrix. Using a ratio of N:C=0.20 resulted in higher biohydrogen production and higher exoelectrogenic activity, generating a maximum power output of 361±157 mW m-2 and 2.39±0.13 mW m-2, respectively. This study provided additional insight in improving the electron transfer efficiency, which could be used to further optimise photo-BESs as part of future research and development for sustainable technologies.
44

Optimizing electrogenic activity from photosynthetic bacteria in bioelectrochemical systems

Call, Toby Primo January 2018 (has links)
The aims of this project were to investigate a range of limitations affecting the electrical performance of bioelectrochemical systems (BES) and their use as analytical tools. The model cyanobacterium Synechocystis sp. PCC6803 was used to characterize light-driven BESs, or biophotovoltaic (BPV) devices. The phycobilisome (PBS) antenna size was altered to modify light absorption. At low to medium light intensities the optimum PBS antenna size was found to consist of one phycocyanin (PC) disc. Incorporating pulsed amplitude fluorescence (PAM) measurements into the BPV characterization allowed simultaneous comparison of photosynthetic efficiency to EET in Synechocystis. Non-photochemical quenching (NPQ) was investigated as a limiting factor in biophotovoltaic efficiency and was found to be reduced in the PBS antenna-truncated mutants. Fluorescence and electrochemical data were combined to develop a framework for quantifying the efficiency of light to bioelectricity conversion. This approach is a first step towards a more comprehensive and detailed set of analytical tools to monitor EET in direct relation to the underlying photosynthetic biology. A set of metabolic electron sinks were deleted to remove a selection of pathways that might compete with extracellular electron transfer (EET). The combined deletion of a bi-directional hydrogenase - HoxH, nitric oxide reductase - NorB, cytochrome-c oxidase - COX, bd-quinol oxidase - cyd, and the respiratory terminal oxidase - ARTO, roughly doubled light driven electron flux to EET. Deletion of nitrate reductase - NarB, and nitrite reductase - NirA, increased EET to a similar degree, but combination with the other knockouts compromised cell viability and did not increase output further. In addition to Synechocystis, the purple non-sulphur α-proteobacterium Rhodopseudomonas palustris CGA009 was used to test the effect of storage molecule synthesis knockout in a more industrially relevant organic carbon source driven BES, or microbial fuel cell (MFC). However, the removal of glycogen and poly-ß-hydroxybutyrate (PHB) did not have a significant effect on electrical output. Finally, the importance of electrode material and design for cell to anode connections in an MFC was investigated. EET from R. palustris was greatly enhanced using custom designed graphene and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) aerogels. Pristine graphene is also shown for the first time to be a viable, low cost alternative to platinum as a cathodic catalyst. Together, these results present a holistic view of major limitations on electrical output from BESs that may contribute to enhancing EET for power generation from MFCs in the long term, and optimization of BPV devices as reliable analytical tools in the short term.
45

Energy and the Environment: Electrochemistry of Electron Transport Pathways in Anode-Respiring Bacteria and Energy Technology and Climate Change in Science Textbooks

January 2016 (has links)
abstract: The finite supply of current energy production materials has created opportunities for the investigation of alternative energy sources in many fields. One example is the use of microorganisms in bioenergy applications, such as microbial fuel cells. Present in many types of environments, microorganisms with the ability to respire solid electron acceptors have become of increasing relevance to alternative energy and wastewater treatment research. In this dissertation, several aspects of anode respiration are investigated, with the goal of increasing the limited understanding of the mechanisms of electron transport through the use of advanced electrochemical methods. Biofilms of Geobacter sulfurreducens, the model anode respiring organism, as well as its alkaliphilic relative, Geoalkalibacter ferrihydriticus, were investigated using chronoamperometry, electrochemical impedance spectroscopy, and cyclic voltammetry. In G. sulfurreducens, two distinct pathways of electron transport were observed through the application of advanced electrochemical techniques on anode biofilms in microbial electrochemical cells. These pathways were found to be preferentially expressed, based on the poised anode potential (redox potential) of the electrode. In Glk. ferrihydriticus, four pathways for electron transport were found, showing an even greater diversity in electron transport pathway utilization as compared to G. sulfurreducens. These observations provide insights into the diversity of electron transport pathways present in anode-respiring bacteria and introduce the necessity of further characterization for pathway identification. Essential to science today, communication of pressing scientific issues to the lay audience may present certain difficulties. This can be seen especially with the topics that are considered socio-scientific issues, those considered controversial in society but not for scientists. This dissertation explores the presentation of alternative and renewable energy technologies and climate change in undergraduate education. In introductory-level Biology, Chemistry, and Physics textbooks, the content and terminology presented were analyzed for individual textbooks and used to evaluate discipline-based trends. Additional extensions were made between teaching climate change with the active learning technique of citizen science using past research gains from studies of evolution. These observations reveal patterns in textbook content for energy technologies and climate change, as well as exploring new aspects of teaching techniques. / Dissertation/Thesis / Doctoral Dissertation Biological Design 2016
46

Engineering the sequestration of carbon dioxide using microalgae

Powell, Erin E 08 April 2010
With greenhouse gas emissions (of which CO2 is the major component) being a major environmental concern, mitigation of those emissions is becoming increasingly imperative. The ability to use a fast growing, photosynthetic organism like microalgae that can survive primarily on nutrients such as sunlight and air (with increased CO2 levels) makes it a desirable agent for CO2 sequestration. The primary goal of this project is the engineering of the sequestration of CO2 using the cultivation of the microalgae species <i>Chlorella vulgaris</i>. Secondary goals of the project are the exploration and development of valuable by-products of the cultivation and the determination of whether utilizing microalgae to capture CO2 could be integrated economically into an industrial facility.<p> The batch growth kinetics of the photosynthetic algal species <i>C. vulgaris</i> were investigated using a well-mixed stirred bioreactor. The growth rate was found to increase as the dissolved CO2 increased to 150 mg/L (10% CO2 by volume in the gas), but fell dramatically at higher concentrations. Increasing the radiant flux also increased growth rate. With a radiant flux of 32.3 mW falling directly on the 500 mL culture media, the growth rate reached up to 3.6 mg of cells/L-h. Both pH variation (5.5 - 7.0) and mass transfer rate of CO2 (KLa between 6 h-1 and 17 h-1) had little effect on growth rate.<p> The operation of continuously stirred tank bioreactors (CSTBs) at minimum cost is a major concern for operators. In this work, a CSTB design strategy is presented where impeller stirring speed and aeration rate are optimized to meet the oxygen demand of growing cells, simultaneously minimizing the capital and operating cost. The effect of microbial species, ions in the culture medium, impeller style, as well as changing CSTB size and biomass input density on the optimum operating conditions, is examined. A study of the effects of various parameters on the CSTB design is shown.<p> Using the kinetic data collected in the batch growth study, a novel external loop airlift photobioreactor (ELAPB) was designed and tested. A model was developed for <i>C. vulgaris</i> growth in the ELAPB that incorporated growth behaviour, light attenuation, mass transfer, and fluid dynamics. The model predicts biomass accumulation, light penetration, and transient CO2 concentrations, and compares predictions to experimental data for radiant fluxes of 0.075 1.15 W/m2 and 0 20% CO2 enrichment of feed air, with a 10% average error. The effect of radiant flux and CO2 concentration is presented with discussion of radial and vertical profiles along the column. For a fed-batch culture at a biomass density of 170 mg/L, the penetration of the radiant flux was found to decrease by 50% within the first 1 cm, and 75% at 2 cm. Theoretical optimum growth conditions are determined to be 0.30 W/m2 and 6% CO2 enrichment of inlet feed air.<p> The algal culture was observed to be a workable electron acceptor in a cathodic half cell. A net potential difference of 70 mV was achieved between the growing <i>C. vulgaris</i> culture acting as a cathode and a 0.02 M potassium ferrocyanide anodic half cell. Surge current and power levels of 1.0 µA/mg of cell dry weight and 2.7 mW/m2 of cathode surface area were measured between these two half cells. The recently developed photosynthetic cathode was also coupled to a fermentative anode to produce a completely microbial fuel cell. Loading effects and the effect of changing culture conditions on fuel cell operation are reported. The maximum power output measured was 0.95 mW/ m2 at 90 V and 5000 ohms. A significant increase in this output is achieved with the addition of supplemental glucose to the anodic half cell and the enrichment of the feed air bubbled into the cathodic half cell with 10% CO2.<p> Two economic feasibility studies were performed on the integration of ELAPBs into an industrial facility. These integration studies operated the ELAPBs continuously as biocathodes in coupled microbial fuel cells (MFCs) that capture CO2 from an existing 130 million L/yr bioethanol plant, while generating electrical power and yielding oil for biodiesel to provide operational revenue to offset costs. The anodes for the coupled MFCs are the existing yeast batch fermentors, and the CO2 to be sequestered comes from the existing bioethanol production. Two different design schemes were evaluated, in both cases the maximum profit was achieved with the maximum number of tall columns operated in parallel. The first design evaluated a batch bioethanol facility with off-site oil processing, and the economic feasibility is demonstrated by the positive Net Present Worth achieved over the 20 year life of the plant, at a 10% rate of return on investment. The second design, for a continuous bioethanol operation, processes both oil and algae biomass on-site, but the economics of this second process are only positive (Internal Rate of Return 9.93%.) if the government provides financial assistance in the form of generous carbon credits (a speculative $100 per tonne of CO2 not yet attained) and a 25% capital equipment grant.
47

Engineering the sequestration of carbon dioxide using microalgae

Powell, Erin E 08 April 2010 (has links)
With greenhouse gas emissions (of which CO2 is the major component) being a major environmental concern, mitigation of those emissions is becoming increasingly imperative. The ability to use a fast growing, photosynthetic organism like microalgae that can survive primarily on nutrients such as sunlight and air (with increased CO2 levels) makes it a desirable agent for CO2 sequestration. The primary goal of this project is the engineering of the sequestration of CO2 using the cultivation of the microalgae species <i>Chlorella vulgaris</i>. Secondary goals of the project are the exploration and development of valuable by-products of the cultivation and the determination of whether utilizing microalgae to capture CO2 could be integrated economically into an industrial facility.<p> The batch growth kinetics of the photosynthetic algal species <i>C. vulgaris</i> were investigated using a well-mixed stirred bioreactor. The growth rate was found to increase as the dissolved CO2 increased to 150 mg/L (10% CO2 by volume in the gas), but fell dramatically at higher concentrations. Increasing the radiant flux also increased growth rate. With a radiant flux of 32.3 mW falling directly on the 500 mL culture media, the growth rate reached up to 3.6 mg of cells/L-h. Both pH variation (5.5 - 7.0) and mass transfer rate of CO2 (KLa between 6 h-1 and 17 h-1) had little effect on growth rate.<p> The operation of continuously stirred tank bioreactors (CSTBs) at minimum cost is a major concern for operators. In this work, a CSTB design strategy is presented where impeller stirring speed and aeration rate are optimized to meet the oxygen demand of growing cells, simultaneously minimizing the capital and operating cost. The effect of microbial species, ions in the culture medium, impeller style, as well as changing CSTB size and biomass input density on the optimum operating conditions, is examined. A study of the effects of various parameters on the CSTB design is shown.<p> Using the kinetic data collected in the batch growth study, a novel external loop airlift photobioreactor (ELAPB) was designed and tested. A model was developed for <i>C. vulgaris</i> growth in the ELAPB that incorporated growth behaviour, light attenuation, mass transfer, and fluid dynamics. The model predicts biomass accumulation, light penetration, and transient CO2 concentrations, and compares predictions to experimental data for radiant fluxes of 0.075 1.15 W/m2 and 0 20% CO2 enrichment of feed air, with a 10% average error. The effect of radiant flux and CO2 concentration is presented with discussion of radial and vertical profiles along the column. For a fed-batch culture at a biomass density of 170 mg/L, the penetration of the radiant flux was found to decrease by 50% within the first 1 cm, and 75% at 2 cm. Theoretical optimum growth conditions are determined to be 0.30 W/m2 and 6% CO2 enrichment of inlet feed air.<p> The algal culture was observed to be a workable electron acceptor in a cathodic half cell. A net potential difference of 70 mV was achieved between the growing <i>C. vulgaris</i> culture acting as a cathode and a 0.02 M potassium ferrocyanide anodic half cell. Surge current and power levels of 1.0 µA/mg of cell dry weight and 2.7 mW/m2 of cathode surface area were measured between these two half cells. The recently developed photosynthetic cathode was also coupled to a fermentative anode to produce a completely microbial fuel cell. Loading effects and the effect of changing culture conditions on fuel cell operation are reported. The maximum power output measured was 0.95 mW/ m2 at 90 V and 5000 ohms. A significant increase in this output is achieved with the addition of supplemental glucose to the anodic half cell and the enrichment of the feed air bubbled into the cathodic half cell with 10% CO2.<p> Two economic feasibility studies were performed on the integration of ELAPBs into an industrial facility. These integration studies operated the ELAPBs continuously as biocathodes in coupled microbial fuel cells (MFCs) that capture CO2 from an existing 130 million L/yr bioethanol plant, while generating electrical power and yielding oil for biodiesel to provide operational revenue to offset costs. The anodes for the coupled MFCs are the existing yeast batch fermentors, and the CO2 to be sequestered comes from the existing bioethanol production. Two different design schemes were evaluated, in both cases the maximum profit was achieved with the maximum number of tall columns operated in parallel. The first design evaluated a batch bioethanol facility with off-site oil processing, and the economic feasibility is demonstrated by the positive Net Present Worth achieved over the 20 year life of the plant, at a 10% rate of return on investment. The second design, for a continuous bioethanol operation, processes both oil and algae biomass on-site, but the economics of this second process are only positive (Internal Rate of Return 9.93%.) if the government provides financial assistance in the form of generous carbon credits (a speculative $100 per tonne of CO2 not yet attained) and a 25% capital equipment grant.
48

Modulation de l'interface entre biofilms microbiens électroactifs et surface d'électrode : modifications de surface et effets de milieux / Interface modulation between electroactive microbial biofilms and the surface of the electrode : surface modification and effect of the media

Smida, Hassiba 13 December 2017 (has links)
Les piles à combustible microbiennes (PCMs) sont des dispositifs bio-électrochimiques qui utilisent des biofilms bactériens électroactifs afin de catalyser des réactions d'oxydoréduction anodique et/ou cathodique pour générer de l'énergie électrique. Afin de promouvoir le développement et la connexion des biofilms, points clé dans les performances des PCM, la surface de l'anode de graphite est fonctionnalisée par des unités pyridine. Celles-ci sont greffées de façon covalente via la réduction électrochimique de cations diazopyridinium, formés in situ à partir de précurseurs amine, en s'inspirant de la méthode d'électrogreffage des sels d'aryle diazonium. Cela permet d'obtenir une interface très robuste. En comparant la réactivité de différents dérivés aminopyridine et les propriétés des couches greffées résultantes, la réduction des cations para-diazopyridinium conduit à des films fins et compacts, bien adaptés pour favoriser l'adhésion bactérienne et le transfert d'électrons entre la surface de l'anode et les bactéries électroactives. La présence d'unités pyridine immobilisées en surface de l'anode permet un développement plus rapide du biofilm et des performances accrues de la PCM pour des biofilms jeunes. Par comparaison, une anode modifiée par des multicouches de polyphénylène puis colonisée par un biofilm bactérien se révèle moins efficace pour la catalyse de l'oxydation de l'acétate. La nature et les propriétés physicochimiques de l'électrolyte sont également un paramètre important dans le développement du biofilm bactérien. Les liquides ioniques à température ambiante présentent des propriétés uniques, notamment en termes de solvatation, et leur utilisation dans des applications biotechnologiques a récemment émergé. Toutefois, leurs effets sur les biofilms bactériens restent encore peu connus. L'ajout d'une sélection de liquides ioniques hydrophiles et hydrophobes à base de cations imidazolium ou pyridinium dans l'anolyte, même en très faible quantité, ou immobilisés à la surface de l'anode inhibe le développement du biofilm. / Microbial Fuel Cells (MFCs) are bio-electrochemical devices based on electroactive bacterial biofilms which catalyze the electron transfer both at the anode and cathode to generate electrical power. To enhance the biofilms development and to improve the biofilm-electrode connection, being both key features in the performance of the MFC, the graphite anode was functionalized by pyridine units. In order to ensure a robust interface, pyridine units are grafted covalently through the electrochemical reduction of diazopyridinium cations in situ formed from aminopyridine precursors, following the well-known electrografting method for aryl diazonium salts. By comparing the reactivity of various aminopyridine derivatives and the resulting grafted layers properties, the para-diazopyridinium cations reduction results in a thin and compact layer, which is the best suited for promoting bacterial adhesion and favorable electron transfer between the anode surface and electroactive bacteria. The presence of pyridine units immobilized on the anode surface leads to a faster biofilm development together with increased MFC performances for young biofilms. In contrast, anode modified with polyphenylene multilayers and then colonized by a bacterial biofilm has been proved to be less effective for the catalysis of acetate oxidation. On the other hand, the nature of the electrolyte and the physicochemical properties are also important parameters for the bacterial biofilm development. Room temperature ionic liquids have unique properties, particularly in terms of solvation, and their use in biotechnological applications has recently emerged. However, their effects on bacterial biofilms remain little known. The addition of a selection of hydrophilic and hydrophobic ionic liquids based on imidazolium or pyridinium cations in the anolyte, even in very small quantities, or immobilized at the anode surface inhibited the biofilm development.
49

Caractérisation et optimisation d'une pile à combustible microbienne / Caracterization and optimization of a microbial fuel cel

Lepage, Guillaume 10 December 2012 (has links)
Dans le cadre de ce projet initiant la nouvelle thématique de recherche sur les piles à combustible microbiennes (PCM) au LOCIE, nous tentons de répondre aux problématiques suivantes : Quelles stratégies d'intensification des transferts peuvent être mises en œuvre pour optimiser les efficacités de conversion chimiques et énergétiques des PCM ? Quels sont les moyens de caractérisation et de contrôle des phénomènes mécanistiques inhérents aux réactions bio-électro-chimiques à chaque électrodes ? Dans un premier temps, nous abordons le sujet à travers deux stratégies concrètes d'optimisation en terme d'architecture : l'utilisation d'électrodes poreuses en carbone vitreux réticulé (CVR) pour maximiser l'aire d'électrode active au sein d'un volume donné d'une part, et d'autre part, l'intégration multi-échelle via l'approche constructale, dont l'objectif est de minimiser la résistance à l'écoulement au sein du réacteur. Dans un second temps, nous conduisons une démarche fondamentale qui s'est attaché à identifier et caractériser les mécanismes électrochimiques, via l'évaluation de l'effet de facteurs d'ordre physico-chimiques (température, conductivité, pouvoir tampon et charge organique) et matériels (oxydation du CVR, catalyseur en platine sur la cathode, épaisseur de membrane, aire de cathode) sur le fonctionnement d'une PCM. Cette approche multifactorielle utilise la méthodologie des plans d'expérience via les tables de Tagushi. Des analyses par spectroscopie d'impédance électrochimique visent à apporter une vision complémentaire de notre système. L'analyse des spectres d'impédance des électrodes et du réacteur nous a permis de modéliser les mécanismes électrochimiques en jeu à travers des analogies électriques. / In this project we addressed the two following issues : what transfer intensification strategies can be set up to optimize the chemical and energetic yields in microbial fuel cells ? What are the most relevant methods to characterize and control the bio-electrochemical phenomenon that are taking place ? We first report two strategies regarding the reactor engineering that are (i) the use of reticulated vitreous carbon as high-surface area porous electrodes and (ii) the use of constructal approach as a multi-scale optimization for fluid distribution. Advantages and limits are discussed. In a second part, we address some basic research which aims at identifying and characterizing the electrochemical phenomenon occurring in our reactor and quantifying the effect of various physicochemical (temperature, conductivity, buffer and substrate concentration) and material factors (oxydized RVC, platinized air-cathode, membrane thickness, cathode surface area). This multifactorial analysis was performed using Tagushi experimental plans and electrochemical impedance spectroscopy (IES). IES was successfully used to simulate our electrodes and cell phenomenon based on electrical analogies using resistive and capacitive elements.
50

Synthesis of GaAs nanowires and nanostructures by HVPE on Si substrate. Application to a microbial fuel cell based on GaAs nanowires / Synthèse de nanofils et de nanostructures de GaAs par épitaxie en phase vapeur par la méthode aux hydrures (HVPE) sur substrat silicium. Application des nanofils GaAs aux piles microbiennes

Dong, Zhenning 15 March 2017 (has links)
Nous avons proposé d'étudier le potentiel de l'outil d'épitaxie HVPE (Hydride Vapour Phase Epitaxy) pour la croissance de nanofils de GaAs. La morphologie nanofil permet au matériau épitaxié de libérer les contraintes dans le cas de l’hétéroépitaxie et de mettre en œuvre des procédés de croissance sur des substrats à faible coût comme les substrats de silicium. Dans ce contexte, j’ai effectué la croissance auto-catalysée de nanofils et des nanoobjets de GaAs par HVPE sur substrat silicium. La HVPE utilise des molécules de GaCl synthétisées à l'intérieur du réacteur dans la zone en amont du substrat à haute température (T> 700 °C). La décomposition du GaCl est beaucoup plus difficile entre 600 °C et 700 °C. Dans ce manuscrit des calculs thermodynamiques des constantes d’équilibre de formation du gallium liquide sont donnés et analysés. Les rapports de flux atomiques III/V obtenus sont de 11 à 222, bien plus élevés que les rapports utilisés dans procédés MBE et MOVPE. Ce travail expérimental a été couplé à un travail de modélisation théorique. Une étude de la faisabilité d’utiliser un substrat constitué de nanofils de GaAs comme électrode dans une pile microbienne a également été initiée. / III-V semiconductor nanowires exhibit excellent electrical and optical properties in laterally confined geometry which is very promising for monolithic integration of photonic nanodevices on silicon substrates. Hydride Vapor Phase Epitaxy (HVPE) process growth was therefore developed in this thesis for the growth of GaAs nanowires. This report is organized into two chapters.The first chapter introduces the state-of-the-art of self-catalyzed GaAs nanowires and nano-structures on silicon substrate. We have demonstrated the growth of self - catalyzed GaAs nanowires by HVPE on un-patterned Si (111) substrates at a low temperature of 600 °C with extremely high GaCl/AsH3 flow ratios. A model that explains well the experimental findings was developed. The second part proposes the design of a Microbial Fuel Cell (MFC) prototype based on GaAs nanowire samples. A MFC prototype based on GaAs nanowire and substrate was developed.

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