Dissertationen zum Thema „Liquide ionique (IL)“
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Masmoudi, Abderrazak. „Recyclage du lithium issu des batteries usagées par extraction liquide-liquide dans un milieu liquide ionique“. Thesis, Strasbourg, 2020. http://www.theses.fr/2020STRAE028.
Der volle Inhalt der QuelleA sustainable supply of lithium is essential for the development of modern electrical devices. These devices are based on lithium-ion batteries (LIB), the key element of these LIB is lithium. Recycling is a strategic axis on which the supply of lithium is based in an environmentally and economically sustainable manner. In this context, during this thesis project, our efforts were directed towards the study of lithium recycling by liquid-liquid extraction (LLE). Ionic liquids (ILs) have been used to replace toxic organic solvents. The present work has two practical and theoretical objectives: (i) the development of a new LLE system for the extraction of lithium by combining extractant and IL and (ii) the understanding of the mechanisms of lithium extraction from aqueous media (acids and bases) in an IL medium with different types of extractants (neutrals and acids). Our results showed that it is relatively difficult to design a LLE system capable of directly extracting lithium from a LIB leachate. For this reason, we proposed to extract lithium at alkaline pH, where most of the cations present in the leachate are already removed. The optimal extraction system under these conditions is that using β-diketone in LI. We have demonstrated that this extraction solvent meets most of the requirements of an ideal system for lithium extraction involving IL
Traore, Youssouf. „Perspective nouvelle pour la récupération de l'indium issu des e-déchets par électrodéposition dans les liquides ioniques à température ambiante“. Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00733947.
Der volle Inhalt der QuelleComminges, Clément Troupel Michel. „Électrosynthèse organique en milieu Liquide Ionique“. Créteil : Université de Paris-Val-de-Marne, 2007. http://doxa.scd.univ-paris12.fr:80/theses/th0405091.pdf.
Der volle Inhalt der QuelleComminges, Clément. „Électrosynthèse organique en milieu Liquide Ionique“. Paris 12, 2007. http://www.theses.fr/2007PA120043.
Der volle Inhalt der QuelleModern chemistry needs to develop new eco-friendly processes, in order to lower wastes and byproducts and avoid the use of toxic reagents. In this context, we focused on a new class of solvents which may satisfy these criterions: ionic liquids (IL) and its use in organic electrosynthesis. We have made a physicochemical study to put in light their strength and weakness in electrosynthetic applications. The high viscosity and a medium conductivity are two brakes for the aimed applications. We propose to optimize these two key parameters by a moderate heating of the solution and the addition of a small amount of a cosolvent. Then, we have tested two types of electrochemical reactions in ionic liquids. In oxidation, the Tempo catalysed oxidation of alcohol to corresponding carbonyl compound was successfully adapted in IL and results are as good as in molecular solvents. We also give information on the mechanism, especially on the pH influence on the kinetics and recycling of the catalyst. In reduction, the reaction is the coupling reaction between a benzylic chloride and an acylating reagent, catalysed with nickel complexes, to form benzylketones. The results, a bit lower in IL than in molecular solvents, shows that IL are also adapted for these reactions combining electrochemistry and homogeneous catalysis with transition metals
Chaabene, Nesrine. „Développement d’une microbatterie redox–flow en milieu liquide ionique“. Thesis, Sorbonne université, 2019. https://accesdistant.sorbonne-universite.fr/login?url=http://theses-intra.upmc.fr/modules/resources/download/theses/2019SORUS592.pdf.
Der volle Inhalt der QuelleThe objective of this thesis is to develop a membraneless redox-flow microbattery using ionic liquids (ILs) as electrolytes. Due to their properties, they are well suited for applications related to energy storage. However, they are very sensitive to moisture, expensive, difficult to synthesize and viscous, making their use at an industrial level difficult. A way of overcoming these drawbacks is to mix the IL with a molecular solvent. In this work, we have studied the electrochemical properties of two aprotic and hydrophobic ILs belonging to 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide family and a protic and hydrophilic IL, ethylammonium nitrate (EAN). We have also studied the influence of molecular solvent (γ-butyrolactone, GBL) addition on the physicochemical properties of the mixtures. Physicochemical properties of two eutectic mixtures: ethaline and Menthol-based DES were investigated in order to compare them with an IL commonly used in electrochemical applications. Electrochemical properties of these ILs and their mixtures with GBL had been studied in the presence of different redox couples in order to select two couples to be tested in a microfluidic cell. Electrical characterizations of different membraneless redox-flow batteries have been carried out using these electrolytic media and electroactive species
Wehbie, Moheddine. „Systèmes chélatants organisés pour l'extraction sélective de métaux stratégiques“. Thesis, Montpellier, 2016. http://www.theses.fr/2016MONTT247.
Der volle Inhalt der QuelleThe liquid-liquid extraction is one of the most studied and developed hydrometallurgical processes, particularly in the areas of applications for the extraction and purification of metals of great interest in the sectors of energy and advanced technologies, such as lanthanides and actinides. Many extractants have been developed for the extraction of these metals in the recent decades where the nature, the arrangement, the rigidity and the stereochemistry of chelating sites determine the affinity and selectivity toward the target metals. The study of chelating systems organized on macrocycles has constituted, in particular, the subject of numerous research studies.In this study, the organization of diglycolamide (DGA) and diamide (DA) subunits on Calix-[4]-arene and resorcinarene cavitand was studied for the extraction of rare earth elements (REEs) and uranium (U). A detailed study on the effect of the organization of DGA subunit on the extraction performance of lanthanides, in toluene, showed that the synthesized macrocycles are more efficient and more selective toward heavy rare earths (HREEs) than the light ones (LREEs). A comparative study for the extraction of lanthanides by these macrocycles in ionic liquid medium revealed that the calix-[4]-arene is a better candidate as preorganised platform than the resorcinarene cavitand. Moreover, a detailed study on the chelating capacity of a calixarene functionalized with diamides (DA) was done for the selective extraction of uranium in sulfuric medium, demonstrating that the diamide pattern is more efficient and more selective than its calixarene analogue
Rios, Vera Rafael Manuel. „Étude des propriétés physicochimiques de mélanges de liquide ionique et d’extractants et leurs applications pour la récupération de l’argent“. Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066570/document.
Der volle Inhalt der QuelleSynthesis and characterization of two new cholinium-based ionic liquids, named N-(2-hidroxyethyl)-N,N-dimethyl-N-octylammonium bis(trifluoromethanesulfonyl)imide [C8linCol]+[NTf2]- and N-(2-hidroxyethyl)-N-(2-ethylhexyl)-N,N-dimethyl-ammonium bis(trifluoromethanesulfonyl)imide [C8ramCol]+[NTf2]- has been developed by 1H NMR, 13C NMR, ATR-FTIR y ESI-MS. Properties as the viscous flux activation energy, the volume or the molar entropy have been calculated from the experimental data on density and viscosity. Calculations showed that the ramified ionic liquid possess a higher degree of structural order when compared with the linear ionic liquid. Also, their capacity for the recovery of Ag (I) was determined and an extraction level of 98.6% for the linear and 40.5% for the ramified ionic liquid was found. Maximum extraction was found at pH 5.0 with an important selectivity on the extraction of Ag (I) and Cu (II) towards Fe (III). Ag (I) extraction with a phosphonium-based ionic liquid (2,4,4 dimethyl(penthyl) phosphinate de trihexyl(tetradecyl) phosphonium) was also tested. Extraction tests were developed at different concentration values when dissolved in kerosene or kerosene plus decan-1-ol. An extraction level of 80 to 85% was determined with the different mixtures at a maximum recovery pH of 3.0. Spectroscopic characterization (ATR-IR) showed the protonation of the anion in the ionic liquid forming the acid specie. This specie is probably the responsible for the extraction of silver. The formation of a dimeric specie was found in the 31P NMR and the value of the formation constant was calculated
Pépin, Matthieu. „Glycosylations d'oligosaccharides supportés sur le liquide ionique pour l'homologation sous contrainte moléculaire de cyclodextrines : étude d'un nouveau complexe d'inclusion cyclodextrine/liquide ionique“. Rouen, 2010. http://www.theses.fr/2010ROUES024.
Der volle Inhalt der QuelleThe aim of this work was to improve the homologation methodology for the modification of cyclodextrins (CD) skeleton. After opening of the macrocycle, grafting of an additional saccharidic unit and cycloglycosylation, an expensive functionalized γ-CDs can be obtained from cheap α- or β-CDs. A rigid molecular clamp was grafted on the primary face of the β-CD to limit the redeployment of the oligosaccharide. Ionic liquid (IL) used as liquid support reduced the purification steps to simple liquid/liquid extractions. Two models were studied : IL grafted on the molecular clamp, and IL grafted on the additional saccharidic unit. The later turned to advantage a method of selective α-(1→4) glycosylation developed on a series of model ionic supported carbohydrates. A new CD/IL inclusion complex and the structure of a single crystal of the molecular clamp supported on LI were also described
Suisse, Jean-Moïse. „Electrosynthèse de nanoparticules métalliques en milieu liquide ionique supramoléculaire“. Strasbourg, 2009. http://www.theses.fr/2009STRA6071.
Der volle Inhalt der QuelleThe first section of this thesis describes the synthesis of a new family of ionic liquid crystalline compounds based on imidazolium cations. The study focuses mainly on the mesomorphic behavior of these materials as a function of the molecule backbone (alkyl tail length). All compounds were fully characterized by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction studies. We report also the synthesis, lamellar crystal structure and catalytic activity of the palladium (II) complex of the (deprotonated) carbene form of one of these salts. In addition, we measured the charged carrier mobilities in the mesophase. The molecular design of our ionic liquid crystalline materials has then been modified to incorporate cyanometallate to endow the products with electrochemical properties. The second section of this thesis is devoted to the development of a new route for the preparation of metallic nanoparticles by electrocrystallization. This approach allow direct and accurate control of the reduction process, of the size of the nanoparticles and of their density of nucleation on the substrate. Of particular significance is the demonstration herein that the supramolecular structure of the liquid-crystal phase can be used to influence the morphology of metal nanoparticles deposited by electrochemical reduction
Joly, Florian. „Solubilité et fluoration d’oxydes d’uranium en milieu liquide ionique“. Thesis, Lille, 2019. http://www.theses.fr/2019LIL1R043.
Der volle Inhalt der QuelleIonic liquids (IL) are molten salts with a melting point below 100 °C. They have numerous advantages compared to usual solvents, including a very low vapor pressure and a good thermal stability. In the context of this thesis, we studied IL for the dissolution and fluorination of uranium oxides. This manuscript starts by a bibliographical study presenting the conversion of uranium in the nuclear fuel cycle, the crystal chemistry of uranium fluorides and ends with a general presentation of ionic liquids. In the second chapter, the solubility of two uranium oxides (UO2 and UO3) is studied in IL commonly used in the literature. The most interesting results are obtained at high temperature (180 °C) with [Hbet][NTf2] and [Bumim][PF6]. With the first one, we observe a good solubility of uranium, whereas [Bumim][PF6] allows the fluorination of UO2 yielding uranium tetrafluoride UF4. In the next chapter, we tried to increase uranium oxides solubility in IL using additional molecules. A significant result is the precipitation of hydrated uranium tetrafluoride (UF4.xH2O) from the addition of aqueous hydrofluoric acid. The following chapter studies the formation of UF4 from the UO2-[Bumim][PF6] mixture in ionothermal conditions (180 °C). Thanks to spectroscopic methods (NMR, XANES/EXAFS), we show that the reaction is initiated by traces of water in the system (14 ppm). Hydrolysis of the IL liberates HF and leads to the precipitation of anhydrous UF4. This documents ends with the use of a non-commercial IL [Emim][F(HF)2,3] which stabilizes hydrofluoric acid in its structure. At 100 °C, this fluorinated IL can fully digest all the uranium oxides that we selected
Joly, Florian. „Solubilité et fluoration d’oxydes d’uranium en milieu liquide ionique“. Electronic Thesis or Diss., Université de Lille (2018-2021), 2019. http://www.theses.fr/2019LILUR043.
Der volle Inhalt der QuelleIonic liquids (IL) are molten salts with a melting point below 100 °C. They have numerous advantages compared to usual solvents, including a very low vapor pressure and a good thermal stability. In the context of this thesis, we studied IL for the dissolution and fluorination of uranium oxides. This manuscript starts by a bibliographical study presenting the conversion of uranium in the nuclear fuel cycle, the crystal chemistry of uranium fluorides and ends with a general presentation of ionic liquids. In the second chapter, the solubility of two uranium oxides (UO2 and UO3) is studied in IL commonly used in the literature. The most interesting results are obtained at high temperature (180 °C) with [Hbet][NTf2] and [Bumim][PF6]. With the first one, we observe a good solubility of uranium, whereas [Bumim][PF6] allows the fluorination of UO2 yielding uranium tetrafluoride UF4. In the next chapter, we tried to increase uranium oxides solubility in IL using additional molecules. A significant result is the precipitation of hydrated uranium tetrafluoride (UF4.xH2O) from the addition of aqueous hydrofluoric acid. The following chapter studies the formation of UF4 from the UO2-[Bumim][PF6] mixture in ionothermal conditions (180 °C). Thanks to spectroscopic methods (NMR, XANES/EXAFS), we show that the reaction is initiated by traces of water in the system (14 ppm). Hydrolysis of the IL liberates HF and leads to the precipitation of anhydrous UF4. This documents ends with the use of a non-commercial IL [Emim][F(HF)2,3] which stabilizes hydrofluoric acid in its structure. At 100 °C, this fluorinated IL can fully digest all the uranium oxides that we selected
Néouze, Marie-Alexandra. „Ionogels obtenus par confinement d'un liquide ionique dans une matrice à base de silice“. Montpellier 2, 2005. http://www.theses.fr/2005MON20099.
Der volle Inhalt der QuelleMekki, Soufiane. „Speciation de l’europium trivalent dans un liquide ionique basse température“. Paris 11, 2006. http://www.theses.fr/2006PA112353.
Der volle Inhalt der QuelleSince the nuclear industry is playing an important role in the power production field, a relevant number of problems have been revealed. Indeed, high-level radioactive long-lived nuclear wastes present a real difficulty for nuclear wastes management. Mino actinides, which compose of these wastes, will be radioactive for several thousands of years. For eventual disposal deep underground, their reprocessing needs to be optimized. The extraction process used industrially to separate actinides and lanthanides from metal species characterizing the spent nuclear fuel produce, nevertheless, enormous quantities of contaminated liquid wastes directly issued from the liquid/liquid extraction step. During the last decade, some room-temperature ionic liquid have been studied and integrated into process. The interest on this class of solvent came out from their “green” properties (non volatile, non flammable, recyclable, etc…), but also from the variability of their physico-chemical properties (stability, hydrophobicity, viscosity) as a function of the RTIL chemical composition. Indeed, it has been shown that classical chemical industrial process could be transferred into those media, even more improved, while a certain number of difficulies arising from using traditional solvent can be avoided. In this respect, it could promising to investigate the ability to use room-temperature ionic liquid into the spent special nuclear fuel reprocessing field. The aim of this thesis is to test the ability of the specific ionic liquid bumim Tf₂N to allow trivalent europium extraction. The choice of this metal is based on the chemical analogy with trivalent minor actinides Curium and Americium which are contributing the greatest part of the long-lived high-level radioactive wastes. Handling these elements needs to be very cautious for the safety and radioprotection aspect. Moreover, europium is a very sensitive luminescent probe to its environment even at the microscopic scale. The manuscript is structured with four parts. In a first chapter, we present the main physico-chemical properties of an imidazolium-based ionic liquid family, and then we choose the ionic liquid bumim Tf₂N for the whole thesis and start with the electrochemical study. In the second chapter, we present the study of europium solvation in the ionic liquid media. In the third part, we expose the results concerning TTA solvation ans its complexation with europium in bumim Tf₂N under different conditions. Finally in the last chapter, we present the results obtained for the europium extraction in a three-stage extraction system : water/ bumim Tf₂N /supercritical CO2. This work highlights the potential use of ionic liquids and particularly bunim Tf₂N in the spent nuclear fuel reprocessing. The ability to extract quantitatively a trivalent lanthanide has been demonstrated. This fundamental study can be regarded as a feasibility demonstration to build an ionic liquid-containing extraction system, in the aim of possible large-scale application
Hadef, Bornia. „Emission de champ electronique et ionique : remodelage d'une source electronique, dynamique d'une source ionique a metal liquide“. Toulouse 3, 1987. http://www.theses.fr/1987TOU30117.
Der volle Inhalt der QuelleHadef, Bornia. „Emission de champ électronique et ionique remodelage d'une source électronique, dynamique d'une source ionique à métal liquide /“. Grenoble 2 : ANRT, 1987. http://catalogue.bnf.fr/ark:/12148/cb37606108v.
Der volle Inhalt der QuelleSrour, Hassan. „Développement d’un électrolyte à base de liquide ionique pour accumulateur au Lithium“. Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10160/document.
Der volle Inhalt der QuelleIn lithium ion batteries, the electrolyte plays an important role because its physicochemical and electrochemical properties determine their efficiency. Currently, the used organic electrolytes induce difficulties in the manufacturing and the use of the battery (volatile and flammable components). New electrolytes based on molten salts at room temperature, called ionic liquids, are safer potential candidates (low flammability, low vapor pressure, high flash point) with a wide electrochemical window. The first stage of this PhD was to design new and more efficient synthetic routes, taking into account the environmental requirements (waste minimization, no solvent) and allowing the elaboration of ionic liquids with high purity> 99.5%, compatible with an industrial production. New ionic liquids derived from imidazolium cation were then designed in order to modulate their physicochemical properties, and to optimize their performance in batteries. They were evaluated in various battery technologies (Graphite/LiFePO4) and (Li4Ti5O12/LiFePO4) under different experimental conditions, 298 K and 333 K, when the conventional lithium ion batteries (organic electrolyte) are used only under 313 K. This PhD work has identified the chemical modifications to yield the most promising electrolytes, and highlighted the importance of the study on the understanding of ionic liquid/electrode interphase phenomena
Mazza, Mathieu. „Modification chimique de la cellulose en milieu liquide ionique et CO2 supercritique“. Phd thesis, Toulouse, INPT, 2009. http://oatao.univ-toulouse.fr/7832/1/mazza.pdf.
Der volle Inhalt der QuelleLin, Rongying. „Formulation of electrolytes based on ionic liquids for supercapacitor applications“. Toulouse 3, 2012. http://thesesups.ups-tlse.fr/1895/.
Der volle Inhalt der QuelleEnergy storage is indispensable for the sustainability of our daily energy needs. Without the support of energy storage systems, the over production of energy would be wasted and the shortage of energy would result in consequential disruptions to our daily activities. Electrochemical energy storage (EES) systems serve as one of the distributed energy technologies and are drawing attention in research to address today's industrial and societal challenges for security and sustainability of energy that they can provide. Amongst the EES, Electrochemical capacitors (EC), also known as supercapacitors are emerging to be prospective energy storage devices with high and fast power delivery owing to the simple charge storage mechanism based on electrostatic attraction: the adsorption of the ions of an electrolyte onto the surface area of the active material of the electrodes. The objectives of this thesis are (1) to study the capacitive behaviour of the electrochemical double layer, constituted by the ions of the electrolyte and the charges induced by the application of an external potential at the electrodes, in view to increase the capacitance and (2) to formulate electrolytes based on ionic liquids with the goal to increase the electrochemical window and hence energy density of the ECs. Ionic liquids (ILs) have in recent years emerged as a neoteric genre of electrolytes which offer great varieties of electrochemical as well as physical properties (ionic conductivity, melting points, electrochemical stability, etc. ). In this context, this thesis has been effectuated by SOLVIONIC, a company which specialized in the research and development of ionic liquids and formulation of electrolytes, in collaboration with CIRIMAT in University of Paul Sabatier in Toulouse, France. Results have provided better insights and understanding on the electrolyte/electrode interface in view of increasing the performances of supercapacitors. A new approach of optimizing the electrode/electrolyte interface that allows capacitive energy storage in a widened temperature range from -50°C to 100 °C has also been demonstrated using formulated eutectic mixtures of ionic liquids and architected electrodes
Vanderaspoilden, Stéphanie. „Contribution to the electrochemistry at the 1-butyl-3-methylimidazolium dicyanamide“. Doctoral thesis, Universite Libre de Bruxelles, 2015. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/209124.
Der volle Inhalt der QuelleDeux grandes thématiques fondamentales sont abordées dans ce travail :le comportement de la double couche électrique à l’interface liquide ionique
Doctorat en Sciences
info:eu-repo/semantics/nonPublished
Lin, Zifeng. „Two dimensional materials (graphene and MXenes) for supercapacitor applications“. Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30157/document.
Der volle Inhalt der QuelleThis thesis aims at studying the electrochemical properties of graphene and MXenes materials used as electrode in supercapacitor applications. The first part starts with the graphene synthesis and electrode films preparation. After immersion in a solution of 10wt% ((PIP13)0.5(PYR14)0.5-TFSI) in acetonitrile electrolyte and vacuum drying, a graphene gel film was obtained and electrochemically characterized in (PIP13)0.5(PYR14)0.5-TFSI ionic liquid mixture electrolyte. The combination of high-voltage electrolyte with fully accessible, high surface area graphene film enables to achieve high gravimetric capacitance up to 175 F/g in neat ionic liquid electrolyte. A large operation temperature range from -40 to 80 oC was achieved thanks to the use of (PIP13)0.5(PYR14)0.5-TFSI ionic liquid eutectic mixture which does not show any phase change down to -60°C. In a second part, we processed 2-Dimmensional Ti3C2Tx MXene materials into gel film using a similar approach that we did for graphene. Ti3C2Tx shows extremely high capacitance of 380 F/g and 1500 F/cm3 in 3 M H2SO4 electrolyte, which i) surpass all the reported results for MXenes so far and ii) show at least similar performance than pseudocapacitive materials such as RuO2. Besides, Ti3C2Tx MXene gel films were also studied in neat ionic liquid electrolyte (EMI-TFSI). A capacitance of 80 F/g was achieved with good rate performance, which is today the best performance obtained in neat ionic liquid for these materials. More interestingly, the charge storage mechanism was further studied by in- situ XRD technique. This in-situ study has evidenced two different charge storage mechanism. During negative polarization, the interlayer spacing in MXene flakes increases due to steric effect during EMI+ cation insertion. Differently, the decrease in the interlayer spacing during positive polarization was ascribed to i) electrostatic attraction between the intercalated TFSI- anions and positively-charged Ti3C2Tx surface and/or ii) a steric effect of EMI+ cations de-intercalation. This thesis presents the promising potential for using Graphene and MXenes as electrode materials for supercapacitor, and shed lights on further development of these materials
Resende, de Azevedo Jacqueline. „Etude de la cristallisation d’une nouvelle molécule à efficacité cardiotonique dans un mélange liquide ionique - eau“. Thesis, Ecole nationale des Mines d'Albi-Carmaux, 2014. http://www.theses.fr/2014EMAC0009/document.
Der volle Inhalt der QuelleThe anti-solvent crystallization allows obtaining micro/nanoparticles, but it presents some disadvantages. In the case of new pharmaceutical molecules, as the LASSBio-294, the solubility in water or organic solvents is very low limiting the application of this operation. The use of Ionic Liquids (ILs) as alternative solvents opens new perspectives in pharmaceutical processing through anti-solvent crystallization process. Unlike conventional solvents, ILs are entirely composed of ions. ILs are organic salts, usually liquid at room temperature, and which are composed of a relatively large asymmetric organic cation and of an inorganic or organic anion. ILs derived from imidazolium cation are used as alternative solvents for this drug, water being used as anti-solvent. First, the solubility is measured in 5 ILs, in water and in water/IL mixtures. In pure water, the solubility is very low (5 ppm). However, for some ILs, it is greater than 200 mg/g solution. The results of solubility in water/IL mixtures permit to choose a water/IL ratio leading to a good solid theoretical yield. Then recrystallization is performed with 1-ethyl-3-methylimidazolium methyl phosphonate [emim][CH3O(H)PO2] as the preferred solvent. Antisolvent crystallization represents a class of process characterized by the mixing between a solution and an antisolvent to produce solid particles. The influence of solvent/anti-solvent ratio, initial concentration, and additives is studied. The solids formed and dried in an oven are characterized by laser granulometry, scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, and dissolution test. Despite the decrease of elementary particles size, the agglomeration state of particles does not permit to improve the dissolution rate. The agglomeration is reduced and the dissolution improved by modifying the drying process (spray drying). Moreover, the presence of an enteric polymer during the spray drying process has a significant impact on the structure of the formed agglomerates. These are disaggregated, dispersed and dissolved very quickly
Ferdeghini, Filippo. „Liquides ioniques sous confinement nanométrique unidimensionnel“. Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066440/document.
Der volle Inhalt der QuelleThe idea behind this project is to exploit the 1D nanometric confinement in order to increase the electrolytes ionic conductivity and, thus, the power of the lithium accumulators. We have focus on a specific class of electrolytes, which, owing to their physical and electrochemical stabilities, have been identified as very promising: the Ionic Liquids (ILs). We have confined the ILs in porous systems having a common topology (cylindrical pores macroscopically oriented), but with complementary physico-chemical properties: i) the porous alumina (AAO, hydrophilic interface, pores diameter between 25 and 160 nm) and ii) Carbon NanoTubes based membranes (CNT, hydrophobic interface, pores diameter of 4 nm).We have developed an original microscopic multiscale model, taking into account the complex dynamics of ILs cations: combination of i) fast reorientation dynamics of side alkyl-chains, ii) molecule diffusion within nanometric aggregates spontaneously formed in the ILs and iii) diffusion between the aggregates. This model reproduces in a very robust way the quasi-elastic neutrons scattering data on an extent interval of wave vector (0.1 à 2.5 Å-1) and time (10-1 à 2.103 ps). At this local scale, we do not observe any influence due to the confinement on the dynamics of the ILs confined in the AAO and CNTs. We show however that at microscopic (PFG-NMR) and macroscopic (impedance spectroscopy) scale the ILs confinement within the NTCs allows to obtain a conductivity gain of factor 3. A patent is filed
Karé, Ousmane. „Dynamique des ions dans les cristaux liquides ioniques thermotropes“. Electronic Thesis or Diss., Sorbonne université, 2023. https://accesdistant.sorbonne-universite.fr/login?url=https://theses-intra.sorbonne-universite.fr/2023SORUS507.pdf.
Der volle Inhalt der QuelleThe thesis is part of an ANR project that aims to understand the dynamics of ions within the self-assembled structures of organic electrolytes based on thermotropic ionic liquid crystals. Our first objective is to study ion dynamics within TILC monomers on several spatial and temporal scales. In order to access the dynamics of ion transport in TILCs-based electrolytes on several scales of space and time, the thesis is based on the combination of NMR techniques used at the PHENIX laboratory and quasi-elastic neutron scattering (QENS) that I should do with the SYMNES laboratory in Grenoble at the Institut Laue Langevin (ILL). For NMR measurements, we will use two techniques which are pulsed field gradient NMR and relaxometry. Pulsed field gradient NMR will allow us to probe the dynamics of counter-ions at the micrometric scale and the time scale from 1s to 1ms will also allow us to measure the diffusion coefficient D. As for NMR relalometry, it probes the dynamics at the intermediate scale between the molecular and micrometric scales. Its time scale ranges from 10 μs to 1ns. The QENS technique will allow us to probe dynamics at the molecular scale and at a molecular scale. A time scale from 1ps to 1ns. Our TILC models are new types of organic electrolytes based on thermotropic ionic liquid crystals. These TILCs are made up of a mesogenic center which is naphthalene into which are grafted two carbon chains of 12 carbons each, an anionic group that can be TFSI or SO3 bonded with counterions such as protons, lithium. The last objective is to understand the dynamics of ions within TILC polymers on several spatial and temporal scales in order to compare them with monomers. The complementarity of these techniques will allow us to study not only the dynamics of counters, but also the dynamics of counters. functional groups such as methyl and methylene groups of carbon chains, and also the influence of TFSI and SO3 anionic groups in TILCs
He, Yunfei. „Study on the interfacial properties of surfactants and their interactions with DNA“. Thesis, Paris 11, 2013. http://www.theses.fr/2013PA112112/document.
Der volle Inhalt der QuelleBearing a hydrophilic part and a hydrophobic part, surfactants can adsorb onto interfaces and lower the interfacial tension (γ), thereby enhancing the interfacial properties and leading to the applications in cleaning, surface functionalization, foaming and emulsification. Charged surfactants are also used in biological applications, in particular to extract and purify DNA, or for gene delivery. In this thesis we have studied the adsorption properties of surfactants, both to air/water interfaces and onto DNA to form complexes. The first part of the thesis concentrates on interfacial studies of surfactants. To understand how they work in these applications it is important to know the time-scales of the surfactant adsorption and desorption. Thus it is necessary to investigate the adsorption and desorption kinetics, which are already widely studied. However, traditional studies tend to make many assumptions, for example, extending the applicability of equilibrium relations to non-equilibrium cases. In this dissertation, the adsorption of two different surfactant systems has been investigated, non-ionic surfactant C12E6 and ionic surfactant CTAB with sufficient salt. A single bubble compression measurement combined with a known equilibrium surface tension (γeq) value allows the determination of γ(Γ), which is more accurate than results from traditional methods. The time-dependent surface concentrations are measured, showing that the adsorption is diffusion controlled at short times.Having shown that adsorption is diffusion controlled, we report desorption of surfactants from the air/water interface for different systems. The desorption processes are confirmed not to be purely diffusion-limited, showing the presence of an energy barrier. The energy barrier is influenced by the alkyl chain length, but not the counterion type.In the second part of the thesis we concentrate on DNA/surfactant systems. Although the interaction between cationic surfactant and anionic polyelectrolyte has been extensively studied, there still remains need to further understand the complex system, especially to rationalize the choice of surfactants to reach controllable DNA binding ability and low toxicity to the organism. In this dissertation, we introduced the systematic investigation on the interactions of two cationic surfactants with DNA.The first surfactant used is a cationic gemini surfactant 12-2-12∙2Br. Before using it with DNA a thorough characterization has been carried out. The equilibration of 12-2-12∙2Br onto an air/water interfaces in the absence of electrolyte is very slow. Addition of NaBr hardly affects the adsorption kinetics at short times, during which the adsorption is diffusive. However, the adsorption equilibrates much faster. The micellization of cationic gemini surfactant 12-3-12·2Br has been investigated. The critical micelle concentration (CMC) increases slightly with temperature and decreases with ionic strength. 12-3-12·2Br interacts strongly with DNA, due to the electrostatic attraction between the two and the hydrophobic interactions between alkyl chains. Salt screens the electrostatic attraction, while increasing spacer length of gemini surfactant weakens its interaction with DNA.Another surfactant has also been studied for its DNA binding ability and we present a systematic study on interactions between cationic ionic liquid surfactant [C12mim]Br and DNA by experimental techniques and Molecular Dynamics (MD) simulation. By adding [C12mim]Br, DNA chains undergo compaction, conformational changes, with the change of net charges carried by the DNA/surfactant complex. MD simulation confirms the experimental results
Jebri, Khouloud. „Couplage en liquide ionique pour l'accès à des molécules macrocycliques d'intérêt biologique“. Thesis, Toulouse 3, 2016. http://www.theses.fr/2016TOU30351.
Der volle Inhalt der QuelleThis thesis describes our studies regarding the organic synthesis in ionic liquids allowing the creation of C-C, C-N and C-O bonds. We describe the synthetic approaches of alpha-oxo gamma-thio-esters via the Mukayaima condensation of the enoxysilane of ethyl pyruvate on thioacetals. In the context of a multi-step synthesis strategy in ionic liquid, the synthesis of the starting materials was also carried out in these solvents. We also present an application of ionic liquids in peptide chemistry: cyclopeptides containing biaryl and biaryl ether linkages. These compounds have attracted considerable interest due to the significant biological activities that most of them exhibit, including antimicrobial and cytotoxic activities. We describe the synthetic approaches of macrocyclic peptides from tyrosine derivatives in ionic liquids. Two main strategies are investigated for the synthesis of macromolecules, peptidic coupling from tyrosine derivatives followed by formation of the biaryl ether bridge as key step and macrolactamization of the preformed biaryl ether, using modern coupling agents such as HATU and BOP. A different reactivity was observed in ionic liquids compared to that in conventional molecular solvents. Copper (I) and (II) salts have been used to catalyze the intermolecular diaryl ether coupling reaction in ionic liquids from tyrosine derivatives to obtain isodityrosine units. Ullmann coupling was not effective due to the presence of electronic and steric constraints, while the Chan-Lam coupling proved to be more advantageous and allowed the formation the isodityrosine units with satisfactory yields . In addition, the Chan-Lam has the advantage of using milder operating conditions
Pham, Phuoc Dien. „Synthèses et utilisations de réactifs à base d'étain supportés sur liquide ionique“. Le Mans, 2009. http://cyberdoc.univ-lemans.fr/theses/2009/2009LEMA1020.pdf.
Der volle Inhalt der QuelleTriorganotin derivatives display reat potential as reagents for organic and radical chemistry but their use has been avoided for the synthesis of pharmacologically active substances due to their toxicity and the difficulties of removing tin residues from the products. Efforts to overcome these problems have been made : supporting the triorganotin reagents on an ionic liquid in order to minimize the contamination of the products with tin. Moreover, a simple work-up procedure (extraction, filtration, or distillation) has been also developed thanks to the immobilization of tin reagents on an ionic liquid. New ionic liquid supported tin reagents were synthesized and were applied in 3 fields as follows: 1. Stille cross coupling reactions: High yields of biaryl (Sn residue < 6 ppm) from iodoaryl were obtained under low temperature(35 °C), solvent-free, ligand-free conditions and simple purification techniques (by extraction). Moreover, the tin compound could be recycled up to 5 times without significant loss of reactivity. 2. Catalytic free radical reduction: A variety of alkyl and aryl halides can be reduced in excellent yields (Sn residue was 5–8 ppm) with high selectivity (alkyl vs aryl) to afford the desired products with a simple work-up procedure. The products were easily isolated by a simple filtration step. 3. Solvent-Free Direct Reductive Amination: An organotin reagent supported on an ionic liquid was used as a catalytic reductant (0. 1 mol%) for the solvent-free direct reductive amination of aldehydes and ketones. A convenient work-up procedure (by distillation) has been developed for a wide variety of substrates. This method presents many advantages as the solvent-free reaction conditions and catalytic quantities of highly reactive organotin reagent used facilitate the purification of products, thus minimizing the contamination of the product by tin (Sn residue was 1. 7–2. 5 ppm)
Clousier, Nathalie. „Apport des alginates aux phases liquide ionique supportées : applications en catalyse organométallique“. Caen, 2013. http://www.theses.fr/2013CAEN2052.
Der volle Inhalt der QuelleThis work deals with the application of two marine polysaccharides, chitosan and alginates, as support in supported ionic liquid phases chemistry. Biopolymer beads with various porosities and functionalities were prepared from chitosan and alginate and characterized by analysis of their texture, their specific surface area, their porous volume and their ability to adsorb the ionic liquid. Ionic liquid containing the dissolved catalyst was immobilized on the biopolymer beads by simple physisorption. Catalytic materials based on chitosan or alginates and named BioSILP were applied to two well known catalytic reactions: the palladium catalyzed allylic substitution and the ruthenium catalyzed metathesis reaction. Activity and stability of these catalytic materials were then evaluated. Catalytic materials proved to be compatible with these catalytic reactions and by changing various parameters in the preparation of BioSILP materials and studying their catalytic performance, the main criteria affecting the catalytic activity and recyclability of the material were highlighted
Vallette, Hélène. „Réactions de couplage en liquide ionique : synthèse peptidique et couplage carbone-phosphore“. Rouen, 2006. http://www.theses.fr/2006ROUES052.
Der volle Inhalt der QuelleFirst, we performed peptide coupling reaction of quaternary amino acids. Similar yields as obtained in organic solvents were obtained in this new medium. The products are cleanly obtained after simple extraction. This approach unpublished before our work was applied to the synthesis of di, tetra, octa and cyclopeptides. Coupling without protection was also tested but without success. Second, we perfomed palladium catalysed carbon-phosphorus cross coupling reaction between phosphine borane complexes and aryl iodides in various ionic liquids. An easy extraction of the crude product and a catalyst recycling (3 cycles) were possible in the new medium. To improve the recycling a new ligand having a cationic moiety was prepared. Associated to palladium, this ligand showed a high catalytic activity for carbon-phosphorus cross coupling reaction allowing an efficient recycling of catalyst (6 cycles)
Duchet, Laetitia. „Synthèses de 3,4-dihydropyrimidines, d’oxadiazoles et de polyamines sur phase liquide ionique“. Rennes 1, 2009. http://www.theses.fr/2009REN1S023.
Der volle Inhalt der QuelleThis work was focused on the use of ionic liquid as support. This new concept has been successfully applied to the development of multicomponent synthesis. Thus, a small library of 3,4-dihydropyrimidines, oxadiazoles and polyamines has been synthesized. Owing to their specific and particular physicochemical properties, ionic liquids have been used efficiently as reaction supports. According to this methodology, the purification steps are quite simple by solvent washings with appropriate solvent or by flash-filtration on gel and, the quality of ionic liquid phase bound product is easily evaluated by classical spectroscopic methods at each reaction step. This kind of support has been also used in multi-step synthesis, leading to new 3,4-dihydropyrimidines functionalized by various heterocycles. After a general presentation and an introduction chapter on ionic liquid as a support, the second chapter presents microwave irradiation and the various sources of microwaves. Chapters 3, 4 and 5 describe the synthesis of molecules supported on ionic liquid phase. Successively, chapter 3 explains the synthesis of 3,4-dihydropyrimidines, chapter 4 is focused on the oxadiazole synthesis and chapter 5 presents a novel iterative polyamines synthesis
Jouannin, Claire. „Apport des polysaccharides marins pour la catalyse en phase liquide ionique supportée“. Caen, 2012. http://www.theses.fr/2012CAEN2035.
Der volle Inhalt der QuelleThe objective of this thesis is to evaluate the contribution of marine polysaccharides to the supported ionic liquid catalysis. Alginates and chitosan are the two polysaccharides used to prepare supports with different porosity and functionality. The immobilization of the ionic liquid phase onto the biopolymer supports was performed by two ways: by adsorption and by confinement. Biopolymer supported ionic liquid catalysts (biopolymer-SILCs) were prepared in the form of beads, cylindrical scaffolds and discs, for applications in batch systems as well as in continuous flow. The textural properties, the stability, the ionic liquid and catalyst loadings of the biopolymer-SILCs were determined and the catalytic species identified. The performance and limitations of the biopolymer-SILCs were then evaluated in two model pallado-catalyzed reactions: the allylic substitution of Tsuji-Trost and the hydrogenation of aromatic nitro compounds, this last reaction being performed in aqueous medium. These studies highlight the influence of processing parameters of biopolymer-SILCs on their structure and on their catalytic activity
Bodin, Charlotte. „Etude des dynamiques d’électrolytes à base de liquides ioniques redox pour une application en supercondensateur“. Thesis, Montpellier, 2019. http://www.theses.fr/2019MONTS145.
Der volle Inhalt der QuelleElectrolytes are at the heart of batteries and supercapacitors and their primary role is to conduct ions, and even if their specifications are actually more complex: chemical stability, high cell voltage, high conductivity. However, depending on the design of the molecules that compose the cation and/or anion, their function could be expanded. Ionic liquids are particularly suitable for this functionalization because of their interesting properties as an electrolyte and their ease of synthesis.In the field of supercapacitors, energy density is a technological limitation. To address this, an innovative strategy is the addition of redox molecules to the electrolyte to participate in charge storage. Despite the promise to increase energy densities (or apparent capacities), the use of redox electrolyte faces two clearly identified limitations: (1) the diffusion of redox molecules decreases the coulombic efficiency and (2) the self-discharge is important. One of these possibilities is the use of biredox ionic liquids (2 oxidation-reducing pairs). This thesis work focused on the study of electrolyte dynamics based on redox ionic liquids for supercapacitor application. The effect of the confinement of redox electrolytes in the porosity of carbon electrodes has been studied. Thanks to this, the different interactions as diffusion and adsorption between redox ionic liquids and electrodes are described. The formalism used to understand these different electrochemical dynamics allow us to combine theory and experimentation to go ever further in understanding the interactions of redox ionic liquids as an electrolyte for energy storage
Costa, Cédric. „Influence des ultrasons de puissance sur les procédés électrochimiques en milieu liquide ionique“. Besançon, 2009. http://www.theses.fr/2009BESA2039.
Der volle Inhalt der QuelleIonic liquids are of interest for numerous applications in the field of electrochemistry, particularly for the reduction of metals and actinides. However, several studies revealed some difficulties mainly due to their high viscosity as well as to their pronounced hygroscopic nature. The use of ultrasound can contribute to the resolution of these problems since several. Studies revealed that they lead to a substantial mass transfer increase, to electrode surface activation, and to a significant modification of the characteristics of the obtained deposits. During this study, we developed an experimental device adapted to the electrochemical measurements in ionic liquid media in the presence of ultrasound. The ionic liquids behavior under ultrasound was studied by several methods. Experiments, carried out with several reference electrolytes, revealed that besides improving the mass transfer phenomenon, ultrasound also induce a non-negligible dehydration of the ionic liquids. A darkening of the ionic liquid is however observed during the sonication. ESI-MS analyses reveal that, even after an irradiation of 48h, no ionized or ionisable decomposition product is present in a significant quantity. Finally, preliminary experiments; carried out on uranium at the IPN Orsay, Wghlight the potential applications of sonoelectrochemistry in ionic liquid media for the electrochemical separation of actinides and lanthanides
Zhang, Shaodong. „Polycondensations dans les liquides ioniques“. Phd thesis, Université Pierre et Marie Curie - Paris VI, 2012. http://tel.archives-ouvertes.fr/tel-00839456.
Der volle Inhalt der QuelleLargeot, Céline. „Développement de supercondensateurs carbone/carbone : relation entre la taille des ions de l'électrolyte et la taille des pores de la matière active“. Toulouse 3, 2009. http://thesesups.ups-tlse.fr/529/.
Der volle Inhalt der QuelleThe aim of this work is to study ion/porous carbon interactions in supercapacitor electrodes to improve their electrochemical performances. Titanium Carbide Derived Carbon (TiC-CDC) are microporous carbon with monodisperse porosity. They allowed us to finely study the interactions between electrolyte's ion size and active material pore size during the electrochemical double layer formation in two different kind of electrolyte (organic and ionic liquid). Unlike to traditional views, in order to maximise capacitance, carbon pore size must be close to electrolyte ions size. It was demonstrated that ions adsorbed on carbon's surface are at least partially desolvated. As carbon porosity is well adapted to electrolyte ions size, the capacity is improved of 40 % in acetonitrile and 60 % in ionic liquid. This corresponds respectively to an enhancement by two and by three of the energy of supercapacitors
Dang, Kim Hoang. „Etude de la réaction de transestérification des huiles végétales catalysés par les liquides ioniques en milieu CO2 supercritique“. Thesis, Montpellier 2, 2010. http://www.theses.fr/2010MON20055.
Der volle Inhalt der QuelleBiodiesel, resulting from renewable sources, becomes more and more interesting for environmental reasons and because of the perspective of the shortage of fossil fuels. The main method for the production of biodiesel is the reaction of transesterification of vegetable oil catalyzed by acid, basic or enzymatic catalysts in homogeneous or heterogeneous phase. The purpose of this work is to study a new way of biodiesel production from the rapeseed oil by using an ionic liquid as catalyst and supercritical CO2 as reaction media. The HSO3 functionalized ionic liquids are acid ionic liquid possessing good catalytic properties for the oil transestefication. The lipophilic character of ionic liquid as well as alcohol influences the performance of the reaction. Ethanol and 1-propanol are more reactive than methanol because of their best solubility in the oil. The ionic liquid can be recycled and the separation of the esters of fatty acids takes place by simple settling. The effect of CO2 on the transesterification of rapeseed oil catalyzed by ionic liquids is not clearly positive because of the preferential extraction of the ethanol. However, by adding the ethanol continuously, the influence of CO2 should be more favorable. Supercritical CO2 can be also used to separate esters, glycerol and catalyst at the end of reaction
Ferdjani, Salim. „Comportement des glycosidases en milieu liquide ionique : nouvelles approches de synthèse d'analogues de galactosycéramides“. Nantes, 2011. http://www.theses.fr/2011NANT2049.
Der volle Inhalt der QuelleThis thesis, carried out at the UMR 6204 U3B, concerns studies on glycosidase activity for catalyzing the synthesis of oligosaccharide. A part of this work focuses on the use of these enzymes in presence of ionic liquids (IL), co-solvents which could promote transglycosylation reaction by decreasing the water activity. The synthesis of galactosylceramide (GalCer) chosen here as a target reaction for this study constitutes its second part. The results of our study carried out on three glycosidases have shown a strong decrease of their activity with increasing concentrations of IL. They also indicate a strong correlation between their thermostability, their activity and their stability in ILs. Regarding the synthesis of GalCer, we have essentially limited our study to the aqueous medium. Two acceptors, precursors of ceramide analogues, were chosen. The first, 2-amino-1-thiazolylpropan-1,3-diol, was found to be poorly recognized by glycosidases and only low yield coupling was achieved by a glycosynthase. The second, a cyclic analogue, was designed on the basis of modelling calculations. This acceptor could be synthesized by a stereoselective aldolisation between DHAP and 3-azido-2-(méthylsulfinothioyl) propanal catalyzed by Rham-1-P-aldolase. Toward this goal, we achieved the aldehyde and DHAP preparation andalso produced the Rham-1-P-aldolase but due to time constraints, we could not complete the aldolisation reaction
Balva, Maxime. „Récupération électrochimique en milieu liquide ionique de nanoparticules de platine contenues dans les électrodes de PEMFC“. Thesis, Université de Lorraine, 2017. http://www.theses.fr/2017LORR0375/document.
Der volle Inhalt der QuelleThe platinum nanoparticles used as catalyst in Proton Exchange Membrane Fuel Cells (PEMFCs) represent around the half of the total price of the cell and is one of the limitations for their large scale commercialization. The treatment of spent PEMFC through the recovery of platinum catalyst is a major concern for their development. Usual recovery routes for platinum-containing catalysts are pyro-hydrometallurgical processes that generate pollutant emissions (CO2, NO2). An electrochemical recovery route by coupling electrochemical leaching and electrodeposition in ionic liquids (ILs) is proposed here, more environmentally friendly, performed in "soft" temperature conditions and without any gases emission. Studies of several electrolytes lead us to select BMIMTFSI + BMIMCl melts (bis(trifluorométhylsulfonyl) imidure + 1-butyl-3-méthylimidazolium chloride), due to the complexing ability of chloride against platinum and the good electrochemical stability of the RMIM+ cation. TFSI-, a weakly coordinate anion, allows us to modulate the complexing ability of the electrolyte, which is a key parameter affecting the nature and the electrochemical stability of the Pt complex formed after leaching. The optimal conditions of the leaching and electrodeposition steps have been determined during this work and successfully applied to PEMFC’s electrode. The selected electrolyte, which is weakly hygroscopic, allows the Pt recovery under ambient atmosphere
Dahi, Abdellatif. „Elaboration d'une membrane permsélective par imprégnation d'une structure polymère poreuse avec un liquide ionique“. Rouen, 2012. http://www.theses.fr/2012ROUES015.
Der volle Inhalt der QuelleThe aim of this thesis was the development of new and stable immobilized ionic liquid membranes (IILMs) based on a Matrimid® porous membrane impregnated with ionic liquids (ILs). To improve the retention of IL phase in the pores of the Matrimid® membrane, surfaces were treated with different plasma treatments (CF4, N2 and O2). Using a Matrimid® dense film, chemical composition and topography of plasma treated surfaces were then studied by XPS and AFM, respectively. Aging of plasma treatments was also discussed. The influence of the surface modification on CO2, N2 and O2 gas permeation through the plasma treated films was evaluated. The direct immersion method to prepare our IILMs was examined by infrared spectroscopy. The influence of each plasma treatment on the impregnation speed through the surface of various Matrimid® porous membranes (plasma treated or not), the impregnation rate (uptake mass IL) and the stability of prepared IILMs were analyzed. The IILMs were then tested for two applications: the separation of VOCs by vapor permeation and selective transport of protons as electrolyte membranes for fuel cells (PEMFC). In that case, a detailed study of water and volatile organic compounds sorption in ILs was undertaken at the beginning of these tests
Marins, Jéssica Alves. „Investigation de fluides électrorhéologiques sur la base des matériaux hybrides“. Phd thesis, Université Nice Sophia Antipolis, 2014. http://tel.archives-ouvertes.fr/tel-01005319.
Der volle Inhalt der QuelleBouyahya, Asmaa. „Utilisations originales d'un liquide ionique : catalyseur et support pour la préparation de polymères biodégradables et composant d'une phase stationnaire séparative à base d'une beta-cyclodextrine et d'un polymère ionique“. Thesis, Normandie, 2018. http://www.theses.fr/2018NORMR036/document.
Der volle Inhalt der QuelleIonic liquids, combinations of organic cations and anions, are structured media of several nanometers and have very interesting and flexible properties. Thanks to these properties, ionic liquids have found a place in abundant applications, particularly in organic synthesis. In this thesis we have presented three different uses: i) The first use is based on the use of ILs as a controlled ring-opening polymerization (POC) catalyst for -caprolactone under mild condition. ii) The second use of ionic liquids is based on the synthesis of an innovative organotin catalyst / initiator supported on an ionic liquid for the preparation of a biodegradable polymer. The presence of the IL should make possible the elimination of the catalyst by simple filtration. The biological tests must agree our theory. iii) The third and last application is based on the creation of an original assembly composed of native and permethylated -cyclodextrins, an ionic liquid and a charged polymer. This new association could give access to water-soluble materials with new separation applications
Bouchal, Roza. „Surfactants, Ionic liquids and Ionosilicas : functional ionic systems for supramolecular chemistry and elaboration of materials by design (ion exchange and vectorization)“. Thesis, Montpellier, 2016. http://www.theses.fr/2016MONTT203/document.
Der volle Inhalt der QuelleThis dissertation deals with innovative synthetic materials bearing cationic entities that are guanidinium and ammonium. These cationic entities give interesting and functional properties for each ionic system studied: surfactant, ionic liquid and ionosilica. For this purpose, we investigated two families groups composed of: guanidiniums salts and ionosilica. Regarding guanidiniums salts, we studied the formation and self-assembly behavior of guanidinium surfactants using different measurement techniques (conductivity, surface tension and calorimetry). This remarkable molecular synthon that represents guanidinium was also highlighted as an ionic liquid for the extraction of methyl orange, diclofenac and chromate. As for ionosilicas, although they also have advantageous properties for ion extraction and adsorption of the active ingredients, however their shaping remains a key parameter for targeting their application. In fact, the design of ionosilica material as nanoparticle allows applications extension in the field of nanomedicine. So during this thesis, nanoparticles containing ammonium substructures were synthesized for the first time and used as a nano-vector to deliver an anti-inflammatory drug (diclofenac). Furthermore, with the aim of ionic extraction in continuous flow, materials containing ionic functions as monolith were synthesized from ammonium precursor via sol gel route. This thesis allowed us to find the theoretical, experimental and illustrative elements of the different aspects of materials formation based on cationic entities with remarkable properties that are guanidiniums and ammonium salts
Oumahi, Camella. „Elaboration de catalyseurs hétérogènes en milieu liquide ionique : nanoparticules métalliques (Au et Au-Pd) supportées sur dioxyde de titane“. Thesis, Paris 6, 2014. http://www.theses.fr/2014PA066503/document.
Der volle Inhalt der QuelleThis work deals with the elaboration of heterogeneous catalysts in ionic liquids (ILs). These salts, liquid at room temperature, were chosen because they permit to adjust the solvent properties depending on their chemical composition (imidazolium salts or Deep Eutectic Solvent based on choline chloride and urea). These solvents allowed the synthesis and deposition of Au and Au-Pd nanoparticles (NPs) on TiO2. The IL nature controls the NPs stability in solution, the strength of the metal/support interaction and the nanostructuration of bimetallic particles. The catalysts performances, evaluated by selective hydrogenation, showed an increase in activity of the Au monometallic catalysts after addition of Pd, a promotion of the catalysts activity due to the presence of P residues from the ILs and an inhibition of the activity caused by S species. TiO2 supports were also prepared in DES. The use of this IL, in addition to a specific Ti precursor, led to a textural and structural control of the obtained polymorphs (anatase, rutile or anatase-rutile mixture). The influence of the support type was studied in CO oxidation after Au deposition by urea deposition-precipitation. The most active Au/TiO2 catalysts were obtained with anatase-rutile mixtures, the vicinity between anatase and rutile phases leading to an optimum activity and stability.This work deals with the elaboration of heterogeneous catalysts in ionic liquids (ILs). These salts, liquid at room temperature, were chosen because they permit to adjust the solvent properties depending on their chemical composition (imidazolium salts or Deep Eutectic Solvent based on choline chloride and urea). These solvents allowed the synthesis and deposition of Au and Au-Pd nanoparticles (NPs) on TiO2. The IL nature controls the NPs stability in solution, the strength of the metal/support interaction and the nanostructuration of bimetallic particles. The catalysts performances, evaluated by selective hydrogenation, showed an increase in activity of the Au monometallic catalysts after addition of Pd, a promotion of the catalysts activity due to the presence of P residues from the ILs and an inhibition of the activity caused by S species. TiO2 supports were also prepared in DES. The use of this IL, in addition to a specific Ti precursor, led to a textural and structural control of the obtained polymorphs (anatase, rutile or anatase-rutile mixture). The influence of the support type was studied in CO oxidation after Au deposition by urea deposition-precipitation. The most active Au/TiO2 catalysts were obtained with anatase-rutile mixtures, the vicinity between anatase and rutile phases leading to an optimum activity and stability
Xie, Yuelin. „Electrodeposition of Co, Ni-based Alloys in Ionic Solutions and their Electrocatalytic Propert“. Electronic Thesis or Diss., Sorbonne université, 2023. http://www.theses.fr/2023SORUS560.
Der volle Inhalt der QuelleThe use of fossil energy, one of the main contributors to carbon emissions and a major source of pollution, has become a hot topic of discussion in recent years. Predicted energy shortages and the resulting environmental challenges are forcing mankind to look for alternatives to fossil fuels. Hydrogen is attracting increasing attention as a clean energy source, with high energy density and minimal emissions. It represents a promising, low-carbon energy carrier ready to supplant fossil fuels, particularly in the demanding industrial and transport sectors, where decarbonization is particular difficult to implement. According to existing literature, there are three main methods for producing hydrogen: hydrogen production from (i) fossil fuels, (ii) gasification, and (iii) water splitting. Water electrolysis under renewable resource conditions can practically eliminate carbon emissions, which is a significant difference compared to hydrogen production from fossil fuels (66 gCO2 e/MJ) or gasification (55 gCO2 e/MJ). Clearly, hydrogen production by electrolysis under ideal conditions has the distinct advantage of being environmentally friendly, with a low carbon footprint. Furthermore, water electrolysis offers many advantages, including the production of high-purity hydrogen, the simultaneous production of oxygen as a by-product, and simple installation. Although the hydrogen evolution reaction (HER) by water electrolysis provides numerous advantages for hydrogen production applications, its industrial adoption remains relatively limited, especially behind the production of hydrogen from fossil fuels. One of the main obstacles to its widespread use is the choice of electrocatalytic materials. Precious metals have exceptional electrocatalytic properties; however, their high cost and limited abundance on earth limit their practical application in all industries. Consequently, the search for cost-effective alternatives involving transition metals and the improvement of electrocatalyst performance through alloying and adjustments of surface morphology has emerged as important and dynamic lines of research. A wide range of techniques have been explored for synthesizing transition metal alloys used in electrocatalytic HER. Among these methods, electrodeposition stands out for its streamlined process, ease of implementation, and precise control, making it a versatile choice for large-scale applications. However, the hydrolysis of water during electrodeposition poses a problem. This can be effectively resolved by employing ionic liquids (ILs) as electrolytes, which are becoming increasingly popular due to their wide electrochemical window, high ionic conductivity, and user-friendly characteristics arising from their non-volatile and non-flammable nature. Surprisingly, research on the electrodeposition of alloys in ionic liquids remains relatively scarce. Consequently, combining the electrodeposition of alloy electrocatalysts with ionic liquids represents an attractive avenue to explore. In this work, we address the following questions: (1) Is it possible to prepare transition metal-based alloys by electrodeposition in ionic liquids? (2) What kinds of alloys can be prepared by electrodeposition in ionic liquids? (3) What is the impact of other elements (Co, Zn, Cu) on the HER properties of alloys? (4) How can the HER properties of alloys be enhanced by surface modification (dealloying)?
Lefort, Thibaut. „Réseaux époxy/liquide ionique avec et sans anhydride : Etude des mécanismes de polymérisation et des propriétés diélectriques“. Thesis, Lyon, 2019. http://www.theses.fr/2019LYSEI126.
Der volle Inhalt der QuelleIonic liquids (Ils) are salts exhibiting a low melting temperature (minus 100 °C). They display interesting properties such as good thermal and chemical stabilities and a high ionic conductivity. For example, these properties make them attractive as lubricant, electrolyte or additive in polymer science. In this thesis, ionic liquids are proposed as a solution for charge accumulation occurring in epoxy based insulators of gas insulated substations (GIS), under high voltage direct current (HVDC). An increase of conduction phenomenon is researched in order to reduce charge accumulation on the surface of insulators during their service. The influence of the addition of IL on the polymerisation of the epoxy network and its properties has been evaluated with and without a conventional anhydride hardener, using a phosphonium based IL, known as reactive and initiator of the epoxy polymerisation. Polymerisation mechanisms were identified by nuclear magnetic resonance (NMR) in liquid phase and differential scanning calorimetry (DSC), the networks and their microstructure by dynamic mechanical analysis (DMA), and their morphology by electronic microscopy (SEM or TEM). Finally, dielectric properties were studied by broadband dielectric spectroscopy and DC conductivity measurements and were discussed in function of the architecture of the different networks
Levard, Quentin. „Étude expérimentale et numérique de la décomposition d'un liquide ionique énergétique pour le développement d'un propulseur à monergol vert“. Thesis, Toulouse, ISAE, 2019. http://www.theses.fr/2019ESAE0055.
Der volle Inhalt der QuelleThis study is part of a joint CNES-ONERA project dedicated to research on green propellants for space propulsion. Most attitude and orbit control systems use the catalytic decomposition of hydrazine, which results in catalyst issue and hydrazine handling constraints. CNES has proposed a new family of green monergol based on energetic ionic liquids. These HPGMs (High Performance Green Monopropellant) offer a propulsion system more efficient and less toxic. The final objective of the project is to initiate thermally the ionic energy liquid decomposition in order to eliminate the catalysts. The aim of the thesis is to characterize the ignition and combustion of these innovative monopropellants. This work presents an experimental approach to observe the decomposition of HPGM using two experimental setups. An isolated droplet setup permits to detect of an ignition threshold pressure, but also a first approximation of the regression rate. A second gutter experimental setup extended the pressure range for this measurement, while reducing uncertainty. Finally, a numerical model has been proposed to represent the regression rate of these monopropellants and their combustion in spray
Bendaoud, Amine. „Fluide supercritique et liquide ionique comme plastifiants de polymères biosourcés : application à l'amidon et à l'acétate de cellulose“. Thesis, Saint-Etienne, 2014. http://www.theses.fr/2014STET4017/document.
Der volle Inhalt der QuelleBiopolymers are viable alternatives to the use of conventional plastics derived from fossil fuels resources. In this study, our objective, beyond doing the melt processing ionic liquids plasticized starch and cellulose acetate in laboratory scale microcoumpounder which simulate the performance of a co-rotating twin screw extruder, are to investigate the effects and influence of ionic liquids and water on the intrinsic properties of the materials which are prepared. In general ways, processing with ionic liquids compared with conventional plasticizers, presents: a better interaction with starch and cellulose acetate, a more efficient depressor of glass transition temperature and allows the production of processed materials with efficient crystallinity destruction and plasticization. In the second step, we investigate the effects of supercritical carbon dioxide on the processing of starch with ionic liquid and the effects of the processing pressure, temperature and duration of supercritical carbon dioxide (ScCO2), which is an environmentally-friendly component, on the properties of plasticized starch. The significant results show that ScCO2 is capable of interacting with starch chains and with ionic liquids, so that it may induce a decrease in the glass transition temperature of the plasticized starch
Szymczak, Jonathan. „Contribution à l'électrodéposition en milieu liquide ionique de tellurure de bismuth en vue de son dopage“. Thesis, Université de Lorraine, 2013. http://www.theses.fr/2013LORR0316/document.
Der volle Inhalt der QuelleThermoelectricity has soared up for few years. Currently reserved to niche markets such as informatics or aerospace, devices based on thermoelectric materials could be used in vehicles in order to harness wasted heat. However, the performance of these materials is insufficient for scale up. Among thermoelectric materials, bismuth telluride (Bi2Te3) compounds are the most efficient at room temperature. The purpose of this work was the electrochemical synthesis of doped-Bi2Te3. Rare earth elements being hardly reducible, aqueous medium is unsuitable for their electrodeposition that's why ionic liquids were chosen as electrolytes because of their large electrochemical window. The first part of this PhD work consisted in elaborating the most suitable ionic liquid allowing lanthanum(III) electrochemical reduction. Among ionic liquids tested, 1-ethyl,1-octylpiperidinium bis(trifluoromethylsulfonyl)imide (EOPipTFSI) was selected. In a second part, we defined a bath composition allows reaching a high solubility of precursor salts by using a binary mixture EOPipTFSI:EOPipBr, EOPipBr being the intermediate product of EOPipTFSI synthesis. Then, electrochemical behaviors of several Bi(III)/Te(IV) mixtures were studied. The electrochemical system is complex. Nevertheless, this detailed analytical study led to Bi2Te3 electrochemical synthesis. Finally, the Te(IV)/Te(0) electrochemical system was more deeply studied, the analysis of Te deposits revealed the coatings were composed of single crystalline nanowires. The influence of experimental on nanowire diameter and coatings morphology was studied. These nanowires could be of great interest to prepare Te-Bi core-shell nanostructures
Al, Zohbi Fatima. „Etude de Polyanilines et de nanocomposites Polyaniline/Graphène en milieu liquide ionique protique pour la réalisation de supercondensateurs“. Thesis, Tours, 2016. http://www.theses.fr/2016TOUR4026/document.
Der volle Inhalt der QuelleThe work carried out during this PhD thesis is based on the preparation of conducting polymers such as polyaniline (Pani) and their composites associated with graphene for use as electrode materials for supercapacitors application. This work was first dedicated to the synthesis of new protic ionic liquids (PILs) combining pyrrolidinium (Pyrr+) or imidazolium (Imi+) cations with p-toluene sulfonate (PTS-), hydrogen sulfate (HSO4-) or (+)-camphor-10-sulfonate (Cs-) anion, and the study of their physico-chemicals properties (conductivity, viscosity) in binary mixtures PILs/water. After determining the formulations needed to achieve the optimum of transport properties, the specific capacitance of Pani/HCl in these PILs medium was determined, and we have shown that the performance of symmetrical devices are improved in capacitance, specific energy and specific power (400F/g, 7Wh/kg and 4kW/kg for the higher values) in comparison to those obtained in a H2SO4 1M medium. These PILs mediums were also used as a synthesis medium of Pani. We have shown that the nature of PILs, acting as soft template, could change the electronic, morphological and thermal properties of Pani. An optimum of electronic conductivity of Pani (22 S/cm) was obtained with a synthesis realized in the binary mixture [Imi][HSO4]/water 70/30 generating a fibrillar morphology and a good cyclability (93% capacitance retention over 1000 cycles in H2SO4 1M at 2 A/g). For Pani synthesis in [Pyrr][PTS]/water, a thermal stability gain (360 °C) is obtained thanks to a PTS- doped Pani. Finally, a preliminary study on the preparation of composite Pani/graphene and Pani/graphene oxide was performed. The syntheses of nanocomposites were realized in PILs/water mixtures. The optimization of the composition of the Pani nanocomposites was studied and it was found that a mass ratio of about 15% in weight of graphene or graphene oxide enables to obtain promising nanomaterials with higher electrochemical performances compared with pristine Pani
Oumahi, Camella. „Elaboration de catalyseurs hétérogènes en milieu liquide ionique : nanoparticules métalliques (Au et Au-Pd) supportées sur dioxyde de titane“. Electronic Thesis or Diss., Paris 6, 2014. https://accesdistant.sorbonne-universite.fr/login?url=https://theses-intra.sorbonne-universite.fr/2014PA066503.pdf.
Der volle Inhalt der QuelleThis work deals with the elaboration of heterogeneous catalysts in ionic liquids (ILs). These salts, liquid at room temperature, were chosen because they permit to adjust the solvent properties depending on their chemical composition (imidazolium salts or Deep Eutectic Solvent based on choline chloride and urea). These solvents allowed the synthesis and deposition of Au and Au-Pd nanoparticles (NPs) on TiO2. The IL nature controls the NPs stability in solution, the strength of the metal/support interaction and the nanostructuration of bimetallic particles. The catalysts performances, evaluated by selective hydrogenation, showed an increase in activity of the Au monometallic catalysts after addition of Pd, a promotion of the catalysts activity due to the presence of P residues from the ILs and an inhibition of the activity caused by S species. TiO2 supports were also prepared in DES. The use of this IL, in addition to a specific Ti precursor, led to a textural and structural control of the obtained polymorphs (anatase, rutile or anatase-rutile mixture). The influence of the support type was studied in CO oxidation after Au deposition by urea deposition-precipitation. The most active Au/TiO2 catalysts were obtained with anatase-rutile mixtures, the vicinity between anatase and rutile phases leading to an optimum activity and stability.This work deals with the elaboration of heterogeneous catalysts in ionic liquids (ILs). These salts, liquid at room temperature, were chosen because they permit to adjust the solvent properties depending on their chemical composition (imidazolium salts or Deep Eutectic Solvent based on choline chloride and urea). These solvents allowed the synthesis and deposition of Au and Au-Pd nanoparticles (NPs) on TiO2. The IL nature controls the NPs stability in solution, the strength of the metal/support interaction and the nanostructuration of bimetallic particles. The catalysts performances, evaluated by selective hydrogenation, showed an increase in activity of the Au monometallic catalysts after addition of Pd, a promotion of the catalysts activity due to the presence of P residues from the ILs and an inhibition of the activity caused by S species. TiO2 supports were also prepared in DES. The use of this IL, in addition to a specific Ti precursor, led to a textural and structural control of the obtained polymorphs (anatase, rutile or anatase-rutile mixture). The influence of the support type was studied in CO oxidation after Au deposition by urea deposition-precipitation. The most active Au/TiO2 catalysts were obtained with anatase-rutile mixtures, the vicinity between anatase and rutile phases leading to an optimum activity and stability
Lagoutte, Sébastien. „Nanocomposites polythiophènes/nanotubes de carbone alignés : élaboration, caractérisations et applications aux supercondensateurs en milieu liquide ionique“. Thesis, Cergy-Pontoise, 2010. http://www.theses.fr/2010CERG0459.
Der volle Inhalt der QuelleThe present work concerned the elaboration of electrodes containing electronic conducting polymer and a carpet of aligned carbon nanotubes for supercapacitor applications. In the first part of this work, we put our attention on the choice of our materials and we were able to determine their electrochemical behavior in ionic liquid. Both chosen polymers : poly(3-méthylthiopène) and poly(3.4-diméthylthiophène) possess very diffrent properties in term of capacitance, oxidation potential, resistance or cyclability. In the second part of this work, we optimized the electrochemical synthesis of a nanocomposite poly(3-méthyltiophène)/aligned carbon nanotubes in ionic liquid. The obtained materials offer the property to be "self-supported" and allow using themselves without current collector. And optimization of the conditions of nanocomposites elaboration allows reaching a capacitance of 180 F.g-1 in EMITFSI in 30°C