Litiumin talteenotto luonnon suola-altaista ionisilla nesteillä

Uusiutuvan energian käytön lisääntyminen lisää sähkön varastoinnin tarvetta. Litiumioniakku-jen on todettu olevan oivallisia keinoja varastoida sähköä esimerkiksi sähköautojen energian-lähteeksi. Tästä syystä akkujen kysyntä kasvaa nopeaa tahtia, jolloin nykyiset litiumlähteet ei-vät enää riitä tuottamaan tarpeeksi litiumia kasvavaan tarpeeseen. Tämän vuoksi litiumin tal-teenottoon tulee valjastaa uusia litiumin lähteitä, joiden hyödynnettävyys nykyisellä tekniikalla on pienen litiumkonsentraation ja muiden alkali- ja maa-alkalimetallien läsnäolon takia vaikeaa. Tällä hetkellä litiumia otetaan talteen eniten korkean litiumpitoisuuden luonnon suolajärvistä. Nykyisin käytössä oleva litiumin erotusprosessi on hidas ja sen käyttö pienten litiumkonsent-raatioiden suola-altailla on kannattamatonta. Tehokkaampana talteenottomenetelmänä luonnon suolajärvillä nähdään litiumin selektiivinen uutto ionisilla nesteillä. Menetelmä on todettu toi-mivaksi suolajärvillä, joilla on matala litiumkonsentraatio. Uusien suolajärvien käyttöönotto ei ratkaise kaikkia litiumin talteenottoon liittyviä ongelmia, sillä suolajärvet ovat alttiita ilmastonmuutokselle, eikä niiden litiumvarannot ole ehtymättömät. Merien litiumvarantoja sen sijaan pidetään lähes ehtymättöminä. Litiumin talteenotto meristä on mahdollista ionisia nesteitä ja membraaneja hyödyntävällä elektrodialyysilaitteistolla, jolla litiumia voidaan ottaa talteen myös hyvin pienistä pitoisuuksista. Lisäksi on mahdollista, että litiumin talteenottoon yhdistetään juomaveden valmistus. Tällainen vedenpuhdistusprosessi olisi myös hyvä kestävän kehityksen näkökulmasta.

Extração de ácidos triterpénicos a partir da casca de eucalipto utilizando líquidos iónicos

Os recursos renováveis têm sido um forte alvo de investigação científica nos últimos anos, onde o aproveitamento de biomassa e seus resíduos para a obtenção de compostos de valor acrescentado, combustíveis e energia têm sido abordados no conceito de biorrefinaria integrada. As indústrias de papel geram quantidades significativas de resíduos, nomeadamente a casca de eucalipto que é atualmente queimada para a geração de energia. De forma a valorizar este resíduo, a presente dissertação teve como objetivo extrair compostos triterpénicos, a partir casca externa de Eucalyptus globulus, utilizando solventes de extração alternativos - soluções aquosas de líquidos iónicos (LIs) – para substituir os solventes orgânicos actualmente utilizados. Os ácidos triterpénicos apresentam um elevado interesse na indústria cosmética, farmacêutica e alimentar graças às suas propriedades antiinflamatórias, antitumurais, entre outras. Primeiramente, caracterizou-se a casca externa de Eucalyptus globulus, e posteriormente procedeu-se ao estudo de solubilidade de ácido ursólico (AU, utilizado como molécula modelo) a 25 ºC em soluções aquosas de LIs e surfactantes de modo a selecionar os solventes mais eficientes para a extração. Deste trabalho conclui-se que a capacidade surfactante das soluções aquosas de LIs, particularmente [C4C1im][C8H17SO4], [C16C1im]Cl e [C14C1im]Cl, desempenham um papel fundamental para a solubilização de AU em água, podendo aumentar quase 16000 vezes a sua solubilidade, e permitiu recuperar cerca de 89% deste composto com simples adição de água como anti-solvente. Por fim, compararam-se as quantidades de ácidos triterpénicos extraídas a partir da casca de eucalipto com soluções aquosas de [C14C1im]Cl, metanol e com extração em soxhlet com diclorometano.

Extraction and purification of immunoglobulin G with aqueous biphasic systems

The immune system is able to produce antibodies, which have the capacity to recognize and to bind to foreign molecules or pathogenic organisms. Currently, there are a diversity of diseases that can be treated with antibodies, like immunoglobulins G (IgG). Thereby, the development of cost-efficient processes for their extraction and purification is an area of main interest in biotechnology. Aqueous biphasic systems (ABS) have been investigated for this purpose, once they allow the reduction of costs and the number of steps involved in the process, when compared with conventional methods. Nevertheless, typical ABS have not showed to be selective, resulting in low purification factors and yields. In this context, the addition of ionic liquids (ILs) as adjuvants can be a viable and potential alternative to tailor the selectivity of these systems. In this work, ABS composed of polyethylene glycol (PEG) of different molecular weight, and a biodegradable salt (potassium citrate) using ILs as adjuvants (5 wt%), were studied for the extraction and purification of IgG from a rabbit source. Initially, it was tested the extraction time, the effect on the molecular weight of PEG in a buffer solution of K3C6H5O7/C6H8O7 at pH≈7, and the effect of pH (59) on the yield (YIgG) and extraction efficiency (EEIgG%) of IgG. The best results regarding EEIgG% were achieved with a centrifugation step at 1000 rpm, during 10 min, in order to promote the separation of phases followed by 120 min of equilibrium. This procedure was then applied to the remaining experiments. The results obtained in the study of PEGs with different molecular weights, revealed a high affinity of IgG for the PEG-rich phase, and particularly for PEGs of lower molecular weight (EEIgG% of 96 % with PEG 400). On the other hand, the variation of pH in the buffer solution did not show a significant effect on the EEIgG%. Finally, it was evaluated the influence of the addition of different ILs (5% wt) on the IgG extraction in ABS composed of PEG 400 at pH≈7. In these studies, it was possible to obtain EEIgG% of 100% with the ILs composed of the anions [TOS]-, [CH3CO2]-and Cl-, although the obtained YIgG% were lower than 40%. On the other hand, the ILs composed of the anions Br-, as well as of the cation [C10mim]+, although not leading to EEIgG% of 100%, provide an increase in the YIgG%. ABS composed of PEG, a biodegradable organic salt and ILs as adjuvants, revealed to be an alternative and promising method to purify IgG. However, additional studies are still required in order to reduce the loss of IgG.

Estudo espectroeletroquímico da eletroredução de CO2 em meio de líquidos iônicos

Tese (doutorado)–Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Silanisation de polysaccharides en milieu liquide ionique et réactivité d’un organoalkoxysilane vis-à-vis de nucléophiles simples : vers des hydrogels injectables pour l’ingénierie tissulaire du cartilage

Tissue engineering is a real challenge for the treatment of cartilage pathologies. In this field, biomimetic hydrogels based on natural polymers are among the most commonly used matrices. A hydrogel made of silanized hydroxypropylmethylcellulose (HPMC-Si) is especially promising because it can be injected in cartilaginous lesions by minimally invasive surgery. However, the current synthesis of HPMC-Si is limited by the insolubility of hydroxypropylmethylcellulose (HPMC). This thesis work was focused on finding new synthesis conditions for the design of HPMC-Si hydrogel. In order to obtain a complete solubilization of HPMC and to improve its functionalization by the (3-glycidyloxypropyl) trimethoxysilane (GPTMS), the use of ionic liquids (IL), which are excellent solvents for polysaccharides, was undertaken. The beginning of this study was first devoted to the selection of an IL and then to the development of new reaction conditions. With these new conditions, higher silicon rates were obtained for HPMC modified in ionic liquid medium, however no hydrogel could be formed. The second part was therefore devoted to the synthesis of GPTMS 13C. Indeed, thanks to this radiolabeling, a structural characterization by 13C NMR of the HPMC-Si could be achieved. Finally, the reactivity in organic solvents of three organosilanes, including the GPTMS, was investigated toward nucleophiles representing the common functions found in natural polymers (e.g. -NH2, -OH, -SH). The results of this thesis have provided insights into the GPTMS reactivity in organic medium and thus paves the way to new conditions for the silanization of polysaccharides.

Studies on terpenes solubility in water and deep eutectic solvents diagrams for biomedical applications

The main objectives of this work are the measurement of terpenes solubility in water at different temperatures, and the formulation of Deep Eutectic Solvents based on choline chloride and polycarboxylic acids, that can be used as hydrotropes of aqueous solutions in terpenes, replacing conventional organic solvents. In this work a new experimental methodology was implemented, using dialysis membranes, for the measurement of terpenes solubility in water. Concerning the deep eutectic diagrams formulation, the determination of the melting points of the eutectic mixtures was performed using a visual method. The method used for determining solubilities was previously validated using a well-studied model compound, toluene. The experimental results of terpenes solubilities in water resulted in a very satisfactory coefficients of variation, always below 6%. The experimental solubility data were analysed and the temperature dependence is also studied in a thermodynamic perspective. The compound with the largest solubility dependence with the temperature is geraniol, while thymol presents the smallest. The phase diagrams of DES formulated were quite satisfactory, presenting always eutectic points below to 373.15 K. For some compositions, the systems composed by choline chloride and lactic, or malonic, or myristic acid were liquid at room temperature. In the case of monocarboxylic acids, eutectic is formed at 60% mol of the acid, to dicarboxylic acid is formed at 50% mol of the acid and for tricarboxylic acid these point is formed at 30% mol of the acid. In the future, it will be important to study the effect of DES as hydrotropes in aqueous solutions of terpenes. Furthermore, it would be interesting to study more terpenes in order to assess the effect of the size of the alkyl chain and the structures of the compounds.

Síntese e caracterização do líquido iônico tetrafluoroborato de 1-metil-3-(2,6-(S)-dimetiloct-2-eno)-imidazol como eletrólito para produção de hidrogênio via eletrólise da água

Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water

Introduction

As liquid media at a temperature less than 100 °C that possess some level of ionic conductivity, it is immediately of interest to consider the use of ionic liquids (ILs) as electrolytes to carry out electrochemical processes. This has of course the origins of the modern era of interest in ionic liquids via the work of Wilkes and coworkers in the 1990s [1]. Applications in electrowinning and electrodeposition have developed including processes for a range of metals from copper and zinc to lithium and aluminium [2]. Some metals such as titanium remain, however, stubbornly difficult to electrodeposit [3]. A range of applications in electrochemical devices, including batteries, fuel cells, and solar cells have also emerged and are being thoroughly discussed in Volume 2 (Electrochemistry in ionic liquids. Applications). In parallel to this, there has emerged the need to understand more in detail some important fundamental concepts of electrochemistry as well as the interest on fundamental electrochemical process taking place in an ionic liquid medium and in identifying the ways in which the processes differ, or not, from conventional solvent systems as a result of the highly charged medium [4–6]. Thereby, in this book, special emphasis is placed on showing which aspects of electrochemistry in ionic liquids are different from electrochemistry in conventional solutions. Furthermore, new electrochemical concepts and theories are presented. The book commences with a deep and comprehensive discussion on electrode/electrolyte interface reactions, interface structure, and its critical properties for all electrochemical applications. Chapter 2 discusses these fundamental concepts along with some in situ techniques, such as electrochemical impedance and Fourier transform infrared spectroscopy, cyclic voltammetry, and electrochemical quartz crystal microbalance, suitable for the characterization of electrode/IL interfaces.

Synergistic corrosion inhibition of mild steel in aqueous chloride solutions by an imidazolinium carboxylate salt

Mild steel infrastructure is constantly under corrosive attack in most environmental and industrial conditions. There is an ongoing search for environmentally friendly, highly effective inhibitor compounds that can provide a protective action in situations ranging from the marine environment to oil and gas pipelines. In this work an organic salt comprising a protic imidazolinium cation and a 4-hydroxycinnamate anion has been shown to produce a synergistic corrosion inhibition effect for mild steel in 0.01 M NaCl aqueous solutions under acidic, neutral, and basic conditions; an important and unusual phenomenon for one compound to support inhibition across a range of pH conditions. Significantly, the individual components of this compound do not inhibit as effectively at equivalent concentrations, particularly at pH 2. Immersion studies show the efficacy of these inhibitors in stifling corrosion as observed from optical, SEM, and profilometry experiments. The mechanism of inhibition appears to be dominated by anodic behavior where dissolution of the steel, and in particular the pitting process, is stifled. FTIR spectroscopy provides confirmation of a protective interfacial layer, with the observation of interactions between the steel surface and 4-hydroxycinnamate.

Étude sur les propriétés physicochimiques et électrochimiques des liquides ioniques redox et leur application en tant qu’électrolyte dans les supercapaciteurs

Ce mémoire porte sur les recherches et les développements dans le domaine des électrolytes à base de liquide ionique redox. Une nouvelle famille de liquide ionique redox basée sur le ferrocenylsulfonyl(trifluoromethylsulfonyl) (FcNTf) a été développée et étudiée pour la première fois afin de démontrer le potentiel de ces liquides ioniques dans les dispositifs de stockage d’énergie. En premier lieu, les liquides ioniques redox (RILs) composés de l’anion électroactif et du cation d’alkylimidazolium sont synthétisés et caractérisés. L’impact de la variation des chaînes alkyles du cation sur les propriétés physicochimiques et électrochimiques du RIL a été étudié. À une faible concentration en solution, l’impact du cation a peu d’influence sur l’ensemble des propriétés. Cependant, à haute concentration (>50 % massique) et sans électrolyte de support, la formation de films en oxydation a été observée à l'électrode positive. Ce point est intéressant pour les futures recherches et développements dans le domaine, puisque la variation des chaînes alkyles du cation des liquides ioniques redox et la formation de films lors de l’oxydation du FcNTf est peu connue et comprise en littérature. De plus, l’optimisation des conditions de solution d'électrolyte RIL dans les supercapaciteurs est aussi présentée. En deuxième lieu, la mise en application des RILs dans les supercapaciteurs a été testée. La performance énergétique et le mécanisme d’autodécharge ont été ciblés dans cette étude. En présence de l’électrolyte redox, la contribution des réactions faradaiques permet d'accomplir un gain énergique de 287 % versus les systèmes purement capacitifs. À cause de la formation de film à l’électrode, l’électrolyte redox FcNTf joue un rôle primordial dans la prévention de l’autodécharge versus les liquides ioniques qui étaient connus jusqu’à présent. Finalement, ce mémoire a permis de mieux comprendre les effets structure-propriétés relative aux modifications du cation chez les liquides ioniques redox.

Étude sur les propriétés physicochimiques et électrochimiques des liquides ioniques redox et leur application en tant qu’électrolyte dans les supercapaciteurs

Ce mémoire porte sur les recherches et les développements dans le domaine des électrolytes à base de liquide ionique redox. Une nouvelle famille de liquide ionique redox basée sur le ferrocenylsulfonyl(trifluoromethylsulfonyl) (FcNTf) a été développée et étudiée pour la première fois afin de démontrer le potentiel de ces liquides ioniques dans les dispositifs de stockage d’énergie. En premier lieu, les liquides ioniques redox (RILs) composés de l’anion électroactif et du cation d’alkylimidazolium sont synthétisés et caractérisés. L’impact de la variation des chaînes alkyles du cation sur les propriétés physicochimiques et électrochimiques du RIL a été étudié. À une faible concentration en solution, l’impact du cation a peu d’influence sur l’ensemble des propriétés. Cependant, à haute concentration (>50 % massique) et sans électrolyte de support, la formation de films en oxydation a été observée à l'électrode positive. Ce point est intéressant pour les futures recherches et développements dans le domaine, puisque la variation des chaînes alkyles du cation des liquides ioniques redox et la formation de films lors de l’oxydation du FcNTf est peu connue et comprise en littérature. De plus, l’optimisation des conditions de solution d'électrolyte RIL dans les supercapaciteurs est aussi présentée. En deuxième lieu, la mise en application des RILs dans les supercapaciteurs a été testée. La performance énergétique et le mécanisme d’autodécharge ont été ciblés dans cette étude. En présence de l’électrolyte redox, la contribution des réactions faradaiques permet d'accomplir un gain énergique de 287 % versus les systèmes purement capacitifs. À cause de la formation de film à l’électrode, l’électrolyte redox FcNTf joue un rôle primordial dans la prévention de l’autodécharge versus les liquides ioniques qui étaient connus jusqu’à présent. Finalement, ce mémoire a permis de mieux comprendre les effets structure-propriétés relative aux modifications du cation chez les liquides ioniques redox.

Methods to study the ionic conductivity of polymeric electrolytes using a.c. impedance spectroscopy

Composite polymeric electrolytes of PEO-LiClO4-Al2O3 and PEO-LiClO4-EC were prepared and the ionic conductivity by a.c. impedance was calculated using four different methods, and three kinds of representations of a.c. impedance spectra were adopted. The first is based on the Nyquist impedance plot of the imaginary part (Z") versus the real part (Z') of the complex impedance. The second and the third correspond to the plots of imaginary impedance Z" as a function of frequency (f), and the absolute value (\Z\) and phase angle (theta) as a function of f, respectively. It was found that the values of the ionic conductivity calculated using the three representations of a.c. impedance spectra are basically identical.

Effect of hydrophobic nanopatches within an ionic surface on the structure of liquids

The structures of liquid water and isopropanol have been studied as a function of the size of a hydrophobic patch present in a model hydrophilic surface via molecular dynamics simulations. A significant anisotropy extending into the first few solvent layers is found over the patch which suggests implications for many real-world systems in which nanoscale heterogeneity is found.

Ionic conductivity studies of polymeric electrolytes containing lithium salt with plasticizer

New plasticized polymer electrolytes were synthesized based on poly ethylene oxide (PEO), Poly (N,N-dimethylamino-ethyl-methacrylate) (PDMAEMA), LiN(CF₃SO₂)₂ (LITFSI) as the salt and tetraethylene glycol dimethyl ether(tetraglyme) and EC + PC as plasticizers. The preparation and characterization of the polymer electrolytes were investigated as a function of temperature and various concentrations of LITFSI. Impedance spectroscopy and differential scanning calorimeter (DSC) were used to characterize the effects of various temperature, lithium salt concentration and two plasticizers on conductivity. The complex of PDMAEMA/PEO/LiTFSI/tetraglyme (S2) exhibits higher conductivity (4.74 × 10⁻⁴ S cm⁻¹at 25 °C) than PDMAEMA/PEO/LiTFSI/EC + PC (S1).