21 |
Dispersão de nanopartículas magnéticas em meios complexos biodegradáveis / Dispersion et propriétés colloïdales des fluides magnétiques biodégradablesKern Barreto, Cynara Caroline 27 October 2016 (has links)
Les nanocolloïdes magnétiques sont des dispersions de nanostructures magnétiques dans un liquide porteur. Par la combinaison des propriétés du liquide et des particules magnétiques, ces dispersions peuvent être confinées, déplacées, déformées et contrôlées par l'application d'un champ magnétique externe et ont ainsi de nombreuses applications en nanosciences et les nanotechnologies. Nous avons étudié la dispersion de nanoparticules magnétiques (NPM) dans les solvants eutectiques profonds (DES). Ces solvants, constitués d'un mélange entre un sel d'ammonium (ici le chlorure de choline (Ch) et un donneur de liaison H (ici, l'ethyleneglycol (EG) ou l'urée (U)) ont des propriétés proches des liquides ioniques tout en étant biodégradables. L'un des verrous concernant ces dispersions est la nature des forces impliquées dans la stabilité colloïdale. En effet, on ne peut plus expliquer la stabilité des dispersions dans ces milieux par le modèle DLVO, classiquement utilisé dans l'eau, du fait de leur force ionique élevée. Nous avons dans en premier temps caractérisé soigneusement deux DES (ChEH (1:3) et ChU (1:2) en mol) du point de vue de la densité et viscosité pour des températures entre 20 et 45°C. Ceci nous a permis de montrer la forte association de ces liquides. Un protocole de dispersion de nanoparticules de maghémite (Fe2O3) ou de ferrite mixte (CoxZn1-xFe2O4) est ensuite proposé, et les dispersions sont étudiées par diffusion de rayonnement (lumière et SAXS). Il s'est avéré que les particules les plus petites étaient les mieux dispersées. Enfin, un test de synthèse de NPM dans des solutions d'argile a permis d'obtenir une polydispersité plus faible en sortie de synthèse. / Magnetic nanocolloids are dispersions of magnetic nanostructures in a carrier fluid. Thanks to the original properties of both the liquid and the magnetic particles, these dispersions can be confined, moved, deformed and controlled by applying an external magnetic field. Such dispersions thus have many applications in nanoscience and nanotechnologies.We studied the dispersion of magnetic nanoparticles in deep eutectic solvents (DES). These solvents (DES), obtained by mixing a quaternary ammonium salt (e.g., choline chloride Ch) and a hydrogen bond donor (e.g., ethyleneglycol EG or Urea U) have properties similar to ionic liquids, and are also biodegradable. One of the questions about these dispersions is the nature of the forces implied in colloidal stability, since the DLVO model classically used in water cannot be invoked here due to the very high ionic strength of the solvent.In a first step, we have carefully characterized two DES ((ChEG (1:3) and ChU (1:2) in mol), measuring the density and viscosity for temperatures between 20 and 45°C. We could thus show the high association in these liquids.A protocol to disperse nanoparticles of maghemite (Fe2O3) or mixed ferrite (CoxZn1-xFe2O4) is then proposed, and the obtained dispersions are studied by dynamic light scattering and SAXS. The size polydispersity was reduced by size sorting, and it reveals that the smallest particles are the most easy to disperse in the DES.Last, a synthesis of NMP in clay dispersion was tested and showed promising results with a reduced size polydispersity.
|
22 |
Dépôts électrochimiques d’argent, de palladium et d’alliages argent-palladium en solvants eutectiques profondsRayee, Quentin 13 March 2020 (has links) (PDF)
Le recours aux solvants eutectiques profonds se présente comme une alternative potentielle aux limitations rencontrées en milieux aqueux pour la réalisation de dépôts électrochimiques. La transposition des procédés électrochimiques des milieux conventionnels vers ces nouveaux milieux n’est pas immédiate et nécessite d’entreprendre des études fondamentales visant à comprendre l’impact de la nature des solvants eutectiques profonds sur différents processus survenant à l’interface électrochimique. Dans cette optique, le présent travail examine les mécanismes impliqués dans la formation de dépôts d’argent, de palladium et du mélange Ag-Pd en solvants eutectiques profonds à l’aide de plusieurs techniques voltampérométriques (voltampérométries cyclique, différentielle, alternative, hydrodynamique, à balayage linéaire) et de mesures chronoampérométriques. Le choix du dépôt d’argent a été retenu comme système modèle et a été étendu à la réalisation d’alliage Ag-Pd qui présente un intérêt plus appliqué. Les solvants eutectiques profonds sélectionnés pour cette recherche sont obtenus en mélangeant du chlorure de choline avec de l’urée (ChCl-U) ou avec de l’acide oxalique (ChCl-Ox). Le comportement électrochimique de AgCl en ChCl-U est fortement affecté par la nature de l’électrode. Sur carbone et platine, une importante surtension pour le dépôt à 3D est requise, alors qu’aucune surtension n’est nécessaire sur électrode d’or en raison d’un processus de dépôt à 2D (dépôt en soustension) de l’argent sur l’or. Ce mécanisme de dépôt en sous-tension est peu sensible à la nature du solvant eutectique profond et très similaire à celui obtenu en solution aqueuse avec une concentration équivalente en chlorures. Le recours à des monocristaux a permis d’examiner l’influence de la cristallographie sur le dépôt en sous-tension. Une attention particulière a été portée à la présence de thiourée en milieu ChCl-U et celle-ci affecte profondément les dépôts métalliques d’Ag en modifiant la coordination des espèces Ag(I) et l’adsorption des espèces constitutives du ChCl-U à la surface d’une électrode d’or. Les mesures voltampérométriques du PdCl2 en ChCl-U ont permis de distinguer quatre régions en potentiel où ont lieu respectivement (des potentiels les plus positifs vers les plus négatifs) un dépôt en sous-tension confirmé par des mesures de désorption oxydative de CO, un dépôt à 3D, la formation d’hydrure de palladium (PdHx) et, à des potentiels bien inférieurs, un processus d’inhibition du dépôt. L’utilisation du ChCl-Ox a mis en évidence que la formation de PdHx dépendait du pH apparent du solvant eutectique. L’étude du mélange de AgCl et de PdCl2 a révélé la coexistence de phases distinctes associées à des alliages de différentes compositions formés lors du dépôt électrochimique. Les proportions entre les différentes phases sont très sensibles aux conditions de température, potentiel de dépôt et concentration des précurseurs métalliques, et l’influence de ces différents paramètres est discutée en détail. De plus, un processus de remplacement galvanique de l’argent par le palladium a également été mis en évidence avec l’appui de mesures XPS. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished
|
23 |
Effects of Choline Chloride, Urea and Their Deep Eutectic Solvents on the Modification of LeatherQi, Letian, Fu, Lihong 26 June 2019 (has links)
Content:
The application of split leather is an important issue in leather industry as most of them was not properly treated and wasted. In this study the application of choline chloride (ChCl), urea (U) and corresponding deep eutectic solvents (DES) on the modification of thermal stability and mechanical strength of mink split leather was investigated. TGA and DSC results indicated DES treatment enhanced thermal stability of split leather, and ChCl treatment reduced the stability. While, U treatment provided a kinetic inhibition during the thermal-decomposition. In terms of the mechanical strength, both ChCl and U treatment reduced burst intensity and extended height. While, after DES treatment the burst intensity and extended height increased significantly. In terms of the dosage, 7% DES provided best performance. Results mentioned above illustrated that DES formed by simply mixing ChCl and U provided strong interaction with fiber, enhanced the crosslinks. A hypothesis of [Ch(Urea)]+[Cl(Urea)]- type structure was proposed, as it enabled DES forming strong hydrogen bonds with functional groups on leather fiber, enhancing the crosslinks and therefore improving the thermal stability and mechanical strength. The DES treatment on leather fibers improved their overall performance and thereby broaden their applications.
Take-Away:
1. DES obtained by mixing ChCl and urea presented very different effect in leather treatment, as the thermal stability and physical strength of leather improved significantly after the DES treatment.
2. A hypothesis of [Ch(Urea)]+[Cl(Urea)]- type structure was proposed, illustrating a formation of strong hydrogen bonds between DES and functional groups on leather fiber. This enhances the crosslinks and therefore improves the thermal and mechanical strength of leather.
|
24 |
Model Chemistry Study Of Choline And Urea Based Deep Eutectic SolventsKellat, Libby Nicole 18 December 2018 (has links)
No description available.
|
25 |
Dispozice a metabolismus kanabinoidů. / Disposition and metabolism of cannabinoids.Hložek, Tomáš January 2019 (has links)
This thesis describes in the form of a commentary on own original publications research on the problems of cannabinoids, ie. phytocannabinoids and some synthetic cannabinoids, their pharmacokinetics and effects. The work consists of four thematic areas: the pharmacokinetics of delta-9- tetrahydrocannabinol (THC) and cannabidiol (CBD) in rats, depending on the route of administration; THC concentration time profile in humans (after inhalation) and implications for transport safety; the pharmacokinetic profile of synthetic cannabinoids in rats; extraction and determination of phytocannabinoids in plant material. The first part of the thesis was to determine pharmacokinetic profiles of THC, CBD and combination thereof (1:1 weight ratio) in rats with respect to administration common in humans, i.e. inhalation, oral and subcutaneous administration. THC, its metabolites (11-hydroxy-tetrahydrocannabinol, 11-OH-THC; 11-nor-delta-9- carboxytetrahydrocannabinol, THCOOH) and CBD concentrations in serum and brains of animals were monitored at the 24 hours experimental interval during the study. Except for inhalation administration, co-administration of CBD inhibited THC metabolism (after both oral and subcutaneous), resulting in an increase in THC concentrations in both serum and brain of the rats relative to...
|
26 |
USE OF DILUTE HYDROFLUORIC ACID AND DEEP EUTECTIC SOLVENT SYSTEMS FOR BACK END OF LINE CLEANING IN INTEGRATED CIRCUIT FABRICATIONPadmanabhan Ramalekshmi Thanu, Dinesh January 2011 (has links)
Fabrication of current generation integrated circuits involves the creation of multilevel copper/low-k dielectric structures during the back end of line processing. This is done by plasma etching of low-k dielectric layers to form vias and trenches, and this process typically leaves behind polymer-like post etch residues (PER) containing copper oxides, copper fluorides and fluoro carbons, on underlying copper and sidewalls of low-k dielectrics. Effective removal of PER is crucial for achieving good adhesion and low contact resistance in the interconnect structure, and this is accomplished using wet cleaning and rinsing steps. Currently, the removal of PER is carried out using semi-aqueous fluoride based formulations. To reduce the environmental burden and meet the semiconductor industry's environmental health and safety requirements, there is a desire to completely eliminate solvents in the cleaning formulations and explore the use of organic solvent-free formulations.The main objective of this work is to investigate the selective removal of PER over copper and low-k (Coral and Black Diamond®) dielectrics using all-aqueous dilute HF (DHF) solutions and choline chloride (CC) - urea (U) based deep eutectic solvent (DES) system. Initial investigations were performed on plasma oxidized copper films. Copper oxide and copper fluoride based PER films representative of etch products were prepared by ashing g-line and deep UV photoresist films coated on copper in CF4/O2 plasma. PER removal process was characterized using scanning electron microscopy and X-ray photoelectron spectroscopy and verified using electrochemical impedance spectroscopy measurements.A PER removal rate of ~60 Å/min was obtained using a 0.2 vol% HF (pH 2.8). Deaeration of DHF solutions improved the selectivity of PER over Cu mainly due to reduced Cu removal rate. A PER/Cu selectivity of ~20:1 was observed in a 0.05 vol% deaerated HF (pH 3). DES systems containing 2:1 U/CC removed PER at a rate of ~10 and ~20 Å/min at 40 and 70oC respectively. A mixture of 10-90 vol% de-ionized water (W) with 2:1 U/CC in the temperature range of 20 to 40oC also effectively removed PER. Importantly, etch rate of copper and low-k dielectric in DES formulations were lower than that in conventional DHF cleaning solutions.
|
27 |
Captage du CO2 par des amines en milieu aqueux et non aqueux (solvant eutectique profond) / CO2 capture by amines in aqueous and non-aqueous media (deep eutectic solvent)Mahi, Mohammed Ridha 09 July 2019 (has links)
Ce travail porte sur l'étude de la capacité d'absorption du CO2 par différents types d'amines dissoutes en milieux aqueux et non aqueux. Ce dernier est constitué d'un mélange de chlorure de choline et d'éthylène glycol dans une proportion molaire respectivement de 1 pour 2. Ce solvant, communément appelé "Ethaline", appartient à la catégorie dite des « Solvants à Eutectique Profond » ainsi désignés car leur composition eutectique permet d'obtenir des mélanges généralement liquides à température ambiante. Pour ce faire un appareil d'équilibre liquide-vapeur avec analyse en ligne de la phase vapeur par GC a été réalisé et son fonctionnement validé. Les isothermes d'absorption du CO2 ainsi que la volatilité (composition de la phase vapeur) des mélanges étudiés, avec et sans CO2, ont été déterminées à différentes températures et pour différentes compositions en amines. Le domaine de pression exploré est particulièrement large : du Pascal à 800 kPa. L'étude a montré que la substitution de l'eau par "l'Ethaline" conduit à une capacité d'absorption du CO2 presque identique à celle de la MEA et DEA en solution aqueuse. Par contre dans le cas de la MDEA on observe une capacité d'absorption plus faible en milieu « Ethaline » qu'en milieu aqueux. Les isothermes d'absorption du CO2 des trois classes d'amines en milieu aqueux et non aqueux ont été corrélés par les modèles semi empiriques de (Gabrielsen et al., 2005) initialement établis par ces auteurs pour les solutions aqueuses (un modèle pour les amines primaires et secondaires conduisant à la formation de carbamates en présence de CO2, un modèle pour les amines tertiaires donnant des sels d'ammonium avec le CO2). Nous avons montré que ces deux modèles représentent avec succès les isothermes d'absorption en milieu non aqueux. Les constantes d'équilibre et les enthalpies de réaction qui s'en déduisent montrent que ces dernières sont plus faibles (en valeur absolue) pour la MEA et TMDEA en solution éthaline qu'en solution aqueuse. Dans le cas de la MDEA la nature du solvant n'a qu'une influence minime sur l'enthalpie de réaction. Les valeurs expérimentales des volatilités des amines dans les différents mélanges Amine- CO2 en milieu aqueux ont été corrélées par différents modèles semi-empiriques. Trois modèles thermodynamiques de coefficients d'activité ; le modèle de Wilson, NRTL et UNIQUAC ont été utilisés afin de restituer les données expérimentales de l'équilibre liquide-vapeur des systèmes aqueux d'amines (sans CO2). Une représentation satisfaisante des résultats expérimentaux par les trois modèles a été obtenue / This work focuses on the study of the absorption capacity of CO2 by different types of dissolved amines in aqueous and non-aqueous media. The latter consists of a mixture of choline chloride and ethylene glycol in a molar proportion of 1 to 2 respectively. This solvent, commonly called "Ethaline", belongs to the category called "Deep Eutectic Solvents" so designated because their eutectic composition makes it possible to obtain mixtures that are generally liquid at room temperature. With this aim, a liquid-vapor equilibrium apparatus with on-line analysis of the vapor phase by GC was performed and its operation validated. The CO2 absorption isotherms and the volatility (composition of the vapor phase) of the studied mixtures, with and without CO2, were determined at different temperatures and for different amine compositions. The explored pressure range is particularly large: from 1 Pa to 800 kPa. The study showed that the substitution of water by "Ethaline" leads to a CO2 absorption capacity almost identical to that of MEA and DEA in aqueous solution. On the other hand, in the case of MDEA, a lower absorption capacity is observed in Ethaline than in aqueous medium. In the hypothesis of a use of the DES+amine solvent for CO2 capture in post-combustion process, a decrease of the vapor pressure of the solvent (comparing to that of water+amine) has an advantage because of the low solvent loss due to vaporization in the absorber. The second advantage is most likely a lower effect of equipment corrosion, the third positive point is a lower enthalpy of absorption of MEA and MDEA in (1 ChCl : 2 EG) comparing to aqueous medium, resulting in a possible saving of energy in the regenerator of almost 40%. The disadvantage of the use of amines in "Ethaline" solution is the high viscosity of this solvent which decreases the kinetics of material transfer and reaction with CO2. The CO2 absorption isotherms and the experimental values of the amine volatilities in the different Amine-H2O-CO2 mixtures were well correlated by different semi-empirical models. Three thermodynamic models based on the activity coefficients; the Wilson model, NRTL and UNIQUAC were used to restitute experimental data for the liquid-vapor equilibrium of aqueous amine systems (without CO2). A satisfactory representation of the experimental results by the three models was obtained
|
28 |
Développement de nouveaux solvants de lavage pour l'absorption des Composés Organiques Volatils / Development of new solvents for Volatile Organic Compounds' absorptionMoufawad, Tarek 19 November 2019 (has links)
L(objectif de cette thèse a été de développer de nouveaux solvants d'absorption des composés organiques volatils (COV). Ces derniers sont des polluants atmosphériques primaires généralement utilisés comme solvants et émis directement par les industries. Ils induisent des effets nocifs pour la santé, et certains d'entre eux, sont classés comme cancérogènes. La réduction des émissions de ces polluants reste donc une préoccupation majeure. L'objectif de notre travail a été d'évaluer les solvants eutectiques profonds (DES) comme absorbants pour les COV. Les DES représentent une nouvelle génération de solvants. Ils sont formés par simple mélange de 2 ou plusieurs composés. Ils peuvent être produits à partir de composés économiques, naturels et biodégradables. La préparation de ces solvants est facile et permet une économie d'atome de 100%. Le travail a été divisé en trois parties.La première partie a été consacrée à la caractérisation des propriétés physico-chimiques des DES, telles que la densité et la viscosité. L'analyse des spectres infrarouge des DES et de leurs composés purs a montré une implication des liaisons hydrogène dans la formation des DES. La polarité a été étudiée à l'aide de la sonde Nile red. Enfin, la solubilité de gaz (CO₂, CH₄ and Ar) a été mesurée dans les DES en fonction de la température. La deuxième partie a porté sur l'évaluation de la capacité d'absorption des DES en utilisant la technique d'headspace statique couplée à la chromatographie en phase gazeuse. Ceci nous a permis de déterminer le coefficient de partage gaz/liquide pour les COV dans les DES à différentes températures. L'influence des mélanges de COV sur les capacités d'absorption des DES a été également déterminée. Ces derniers ont montré des capacités d'absorption élevées pour la variété de COV, sans saturation même à forte concentration. Un nouveau système DES-cyclodextrine a également été évalué. Les capacités d'absorption ont été améliorées grâce au rôle de molécule cage de la cyclodextrine. La deuxième partie a été tournée vers l'application industrielle. Nous avons évalué les capacités d'absorption des DES à l'aide d'un montage dynamique qui simule une colonne d'absorption industrielle. Cette installation permet de moduler le débit du COV, les teneurs en eau ainsi que la température de la colonne. Enfin, la régénération des DES a été effectuée par plusieurs cycles absorption/désorption sans perte de capacité d'absorption. En conclusion, l'ensemble des résultats obtenus a montré que les DES possédaient de nombreux atouts leur permettant d'être considérés comme des solvants prometteurs pour l'absorption des COV. / The aim of this thesis was to develop new solvents for the absorption of volatile organic compounds (VOC). VOC are primary air pollutants generally used as solvents and emitted directly from industries. They have adverse health effects and some of them are classified as carcinogenic. Consequently, the reduction of the emissions of these pollutants remains a major challenge to reduce air pollution. Hence, our objective was to evaluate deep eutectic solvants (DES) as absorbents for VOCs. DESs represent a new generation of solvents that is formed by simply mixing two or more compounds. They can be produced from cheap, natural and biodegradable compounds. The preparation of these solvents is easy and is 100% atom efficient. This work was divided into three parts.The first part focused on the physicochemical properties of DES, such as density and viscosity. Analysis of the infrared spectra of DES and their pure compounds showed that hydrogen bonds are essential for the formation of DES. Their polarity was studied using the Nile red probe. In addition, solubility of various gases (CO₂, CH₄ and Ar) was measured as a function of temperature. The second part dealt with the evaluation of the aborsption capacity of DESs using static headspace coupled with gas chromatography. The determination of gas/liquid partition coefficient was performed for various VOC and DES at different temperatures. In addition, the influence of VOC mixtures on DES absorption capacities was determined. DES showed high absorption capacities for a variety of VOCs, without saturation even at high concentration. A new DES-cyclodextrin system was developed and showed improved absorption capacities due to the complexation ability of the cyclodextrin. The last part was oriented towards the industrial application of DESs. The absorption capacities of DESs were evaluated using a dynamic set-up which simulated an industrial absorption column. This set-up allows the modulation of the VOC flow rate, water content and column temperature. Finally, the regeneration of the absorbent was carried out by several absorption/desorption cycles without loss of absorption capacity. In conclusion, the overall results showed that DES have characteristics that allow them to be considered as promising solvents for VOC absorption.
|
29 |
Investigation of Charge Transfer Kinetics in Non–Aqueous Electrolytes Using Voltammetric Techniques and Mathematical ModelingShen, Dai 28 January 2020 (has links)
No description available.
|
30 |
Ionometallurgy for low-temperature metal synthesis from metal oxidesRichter, Janine 14 February 2024 (has links)
Metals and valuable metal compounds are important parts of our everyday lives with applications ranging from aluminum foil over circuit boards to high-performance alloys for engineering and buildings construction. Large-scale metal production processes provide access to metals contained in numerous naturally occurring ores, earths and minerals and should be considered one of the major drivers of industrialization, leading to a continuous increase in living standards. Thereby, metals are often present in the form of oxides or other compounds of low reactivity and high stability. This makes metal extraction an often energy-intensive, environmentally problematic endeavor, relying on high reaction temperatures around 1000 °C or aggressive, corrosive and toxic chemicals.
A disruptive, new approach for more sustainable metal production could be ionometallurgy, i.e., metal extraction by means of ionic liquids (ILs) and deep eutectic solvents (DESs). ILs, per definition, are salts with a melting point below 100 °C, while DESs are eutectic mixtures of two or more reagents with a melting point below that of the individual components. Both classes of materials feature favorable properties,
such as a good solubility for many inorganic salts. Ionometallurgy is a seemingly simple approach, dissolving metal oxides at moderate temperature in an IL or DES and subsequently either electrodepositing the respective metal or producing valuable metal compounds by downstream chemistry.
This thesis elucidated the general feasibility of the direct ionometallurgical metal production from metal oxides in two betaine-based solvents, namely the IL betainium bis(trifluoromethylsulfonyl)imide ([Hbet][NTf2]) and a DES consisting of betaine hydrochloride, urea and glycerol in the molar ratio 1 : 4 : 2.5 ([Hbet]Cl/4U/2.5GLY).
Initial solubility studies involved a broad screening of the reaction behavior of numerous metal oxides with different properties regarding the position of the metal in the periodic table, its oxidation state as well as the basicity of the oxide. Exploiting the Brønsted-acidic functional group of the betainium cation, metal oxide dissolution in this case follows the principle of an acid-base reaction. Correspondingly, [Hbet][NTf2] favors the dissolution of basic or amphoteric metal oxides, while acidic metal oxides remain unaffected. In-depth investigations were performed for the examples of copper, cobalt and aluminum and identified the metal oxide lattice energy, the crystal structure and the reaction temperature as well as complex stabilities of the metal ions as additional factors to influence the solubility. How additives can affect the reaction outcome in multiple ways was shown for the example of chloride. In the copper system, small amounts of chloride act catalytically, while larger concentrations not only decrease the reaction time but also exhibit a structure-directing effect. For cobalt oxides, chloride is assumed to be reaction-driving due to the high chloride affinity of cobalt(II). These results were supported by seven new crystal structures found in the course of these investigations.
Thereby, for the first time, metal oxide dissolution in [Hbet][NTf2] was systematically investigated under water-poor conditions. Abstaining from aqueous IL solutions, although water was shown to promote metal oxide dissolution, enables access to several metals via electrodeposition. This is facilitated by the large electrochemical windows of [Hbet][NTf2] and [Hbet]Cl/4U/2.5GLY, amounting to −2.0–1.4 V and −2.3–0.9 V, respectively. Copper, cobalt, nickel, tin, lead, zinc, and small amounts of vanadium were shown to be electrochemically reducible, whereas manganese, molybdenum and aluminum could not be electrodeposited within the electrochemical stability range of the IL or DES.
For the deposition of the noble metal copper, the chloride content, the deposition temperature and additional organic solvents were identified as crucial parameters for the deposition potential as well as the quality of the deposit. By copper-coating a steel plate, a potentially industrially relevant application was demonstrated. Compared to the conventional industrial process for copper production, this ionometallurgical approach could imply a significant simplification and proceed at much lower reaction temperatures. Starting from tenorite or oxidic copper waste, copper coatings could directly be producible avoiding multiple process steps. Furthermore, the cobalt system revealed, that the thorough understanding of the complex equilibria present in solution is crucial for the successful electrodeposition of the metal. Thus, no deposits were obtained when anionic [CoCl4]2– was the predominant cobalt complex species. The adjustment of the cobalt-to-chloride ratio is a suitable method to generate sufficient amounts of cationic cobalt complexes, allowing for the deposition of the metal.
Overall, several metals were directly produced from their oxides by the ionometallurgical approach at temperatures below 175 ℃. This means a significant temperature reduction compared to the conventional processes. Encouragingly, [Hbet][NTf2] already showed first promising results when applied to industrially relevant starting materials, such as black mass for the recycling of lithium ion batteries or bauxite as a highly relevant, naturally occurring aluminum resource.
While this qualifies ionometallurgy in principle as a considerable improvement regarding process sustainability, the impact of [Hbet][NTf2] and [Hbet]Cl/4U/2.5GLY was analyzed in more depth. Thereby, the recyclability of the solvents is considered a very important factor for the efficient implementation of ionometallurgy in larger scale. First experiments in a two-compartment electrochemical cell showed that metals can be electrodeposited cathodically with a tailorable anode reaction. The oxygen evolution reaction in an aqueous electrolyte proved as suitable benign oxidation reaction in the anode half cell. The intactness of [Hbet][NTf2] after metal
electrodeposition in this set-up was evidenced by NMR spectroscopy, qualifying the IL for reuse in principle.
As opposed to this, decomposition reactions were identified to take place in both the IL and the DES. At 175 °C, [Hbet][NTf2] undergoes the chloride-induced decomposition via a Hunsdieker and a Deacon reaction, which is avoidable by a lower reaction temperature of 150 °C. NMR studies suggest that [Hbet][NTf2] does not decompose during the ionometallurgical process at this temperature. However, in the case of [Hbet]Cl/4U/2.5GLY, NMR and mass spectrometric studies proved the degradation via several decomposition pathways at 60 °C already. These decomposition reactions change the composition of the DES, which also affects the solubility of metal oxides. The thermal and chemical stability of [Hbet][NTf2] and [Hbet]Cl/4U/2.5GLY, besides other factors, have direct implications for their consideration as green solvents. Thus, [Hbet][NTf2] should only be used at reaction temperatures below 150 °C. Furthermore, its industrial application might be impeded by the expensive and toxic [NTf2]– anion. While betaine-based solvents can be easily accessible due to the natural abundance of betaine, the synthesis effort of the [NTf2]–
anion makes [Hbet][NTf2] a considerably expensive IL. [Hbet]Cl/4U/2.5GLY is cheaper and easier to be synthesized from naturally abundant substances, yet not a considerable option due to its decomposition at low temperature already. Its thermal and chemical instability pose hardly surmountable obstacles regarding the recycling and the toxicity of [Hbet]Cl/4U/2.5GLY. Thus, both [Hbet][NTf2] and [Hbet]Cl/4U/2.5GLY do not qualify as green solvents and more benign alternatives should be found in the future.
Altogether, this thesis showed that the ionometallurgical production of metals from their oxides is possible and, moreover, could be a sustainable alternative to conventional processes. The presented investigations extend our understanding of metal oxide chemistry in ILs or DESs and provide proofs of concept, laying a foundation for further work that leaves numerous opportunities for ongoing exploration and optimization. Hence, ionometallurgy could be one step to face the urgent challenge of climate change.
|
Page generated in 0.0854 seconds