Littérature scientifique sur le sujet « Bio-based Ionic Liquid »

The constant utilization of petroleum-based products has prompted concerns about the environment, hence a replacement for these products must be explored. Biolubricants are a suitable replacement for petroleum-based lubricants as they provide better lubricity. Biolubricant performance can be improved by the addition of graphene. However, there are reports that graphene is unable to form a stable suspension for a long period. This study used a graphene-ionic liquid additive combination to stabilize the dispersion in a biolubricant. Graphene and ionic liquid were dispersed into the biolubricant via a magnetic stirrer. The samples were tested using a high frequency reciprocating rig. The cast iron sample was then further observed using various techniques to determine the lubricating mechanism of the lubricant. Different dispersion stability of graphene was observed for different biolubricants, which can be improved with ionic liquids. All ionic liquid samples maintained an absorbance value of three for one month. The utilization of ionic liquid was also able to decrease the frictional performance by 33%. Further study showed that by using the ionic liquid alone, the frictional could only reduce the friction coefficient by 13% and graphene could only reduce the friction by 7%. A smooth worn surface scar can be seen on the graphene-IL sample compared to the prominent corrosive spot on the IL samples and abrasive scars on graphene samples. This indicates synergistic behavior between the two additives. It was found that the ionic liquid does not only improve the dispersion stability, but also plays a role in forming the tribolayer.

Liquid–liquid separations based on countercurrent chromatography, in which at least one phase contains an ionic liquid, represent a new empirical approach for the separation of organic, inorganic, or bio-based materials. A custom-designed instrument has been developed and constructed specifically to perform separations (including transition metal salts, arenes, alkenes, alkanes, and sugars) with ionic liquids, and has been demonstrated for use on the 0.1 to 10 g scale.

Dehydrogenated steroids are usually more effective in treating diseases, compared to their precursors. In this study, toxicity of six ionic liquids to the Arthrobacter simplex was investigated to evaluate the possibility of dehydrogenation of 11α-hydroxy-16,17α-epoxy progesterone in ionic liquid / water biphasic system. Results indicated that ionic liquids displayed higher toxicities to the A. simplex. The followed bio-dehydrogenation in biphasic system, as well as the immobilization investigations in the corresponding system, showed the lower conversion ratio of 11α-hydroxy-16,17α-epoxy progesterone. This maybe indicated the unsuitability of the imidazole-based ionic liquid for the dehydrogenation of A. simplex in the biphasic system.

Ce mémoire est consacré à l’utilisation de l’électrochimie comme outil de synthèse alternatif pour la formation de nouvelles molécules de la famille des azoliums. Une nouvelle méthode de synthèse électrochimique a été mise au point pour la synthèse de carboxylates d’imidazoliums (carbènes masqués) conduisant à une grande variété de molécules. Cette méthode a été comparée aux synthèses chimiques déjà existantes. Dans un contexte actuel de développement durable, des produits bio sourcés ont été synthétisés et à partir de ces derniers l’optimisation du procédé a été réalisée afin de réduire les flux entrants et sortants de matière et d’énergie.Le rôle clé de l’ion hydrogénoxalate a été démontré dans la synthèse de liquides ioniques et/ou sels d’imidazoliums. Certains ont été par la suite employés comme catalyseurs recyclables pour l’estérification de Fischer.La réduction électrochimique directe de différents azoliums a aussi été étudiée. Le couplage des radicaux neutres ainsi électrogénérés conduit aux σ-dimères correspondant. Ce produit redonnant par oxydation l’azolium de départ, la renversabilité de la réaction a été prouvée ouvrant la voie à de nouveaux interrupteurs moléculaires.Une électrosynthèse d’azoliums à fragment aromatique a également été étudiée. Ainsi, l’oxydation électrochimique du pyrène en présence de différents nucléophiles azotés génère les sels d’azoliums pyrène. Ce procédé a été optimisé en termes de réduction de déchets et de simplification de mise en œuvre. Certaines molécules obtenues ont montré des propriétés antimicrobiennes
This work deals with the use of electrochemistry as a tool for alternative synthesis of new azolium-based molecules.A new electrosynthesis method was developed for the synthesis of imidazolium carboxylates (masked carbenes) leading to a wide library of compounds. This approach was compared to already reported chemical syntheses. In the current context of sustainable development, bio based products have been synthesized and optimization of the process was achieved in order to reduce waste and energy consumption.The key role of the hydrogenoxalate anion was demonstrated in the synthesis of ionic liquids and/or imidazolium salts. Some of them were employed as recyclable catalysts for Fischer esterification.The direct electrochemical reduction of various azoliums was also studied. The coupling of two electrogenerated neutral radicals leads to the corresponding σ-dimers. The oxidation of this species gives back the starting azolium proving the “reversibility” of the reaction, paving the way for new molecular switches.Azolium containing pyrene moiety was also electrosynthesized. Thus, electrochemical oxidation of pyrene in presence of different nitrogen nucleophiles leads to azolium pyrenes. This process was optimized in order to reduce waste and simplify the experimental setup. Some products have shown antimicrobial activities

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

[ENG] Global warming, caused mostly by the increasing of greenhouse gas concentrations in the atmosphere, has became one of the most serious environmental concerns. Between the major greenhouse gases, carbon dioxide had the most significant increase. Its high availability, non-flammability, low toxicity and independency from the food supply chain, makes CO2 utilization as a carbon feedstock an important topic from both industrial and academic perspectives. The aim of this work was to develop process intensification strategies for cyclic carbonate production from CO2 and epoxides. Cyclic carbonates are versatile molecules which may become a future platform to introduce CO2 as a renewable carbon feedstock into the chemical sector. Indeed, cyclic carbonates find use in a wide range of applications as electrolytes for lithium batteries, polar aprotic solvents, pharmaceutical intermediates and also as monomers in polymer production. For the first time, zinc (II) complexes of arylhydrazones of β-diketones (AHBD) combined with ionic liquids were used as catalysts for the production of cyclic carbonates. Different cation and anion families were explored in order to understand the effect of specific functional groups on the final reaction yield and selectivity. Results confirmed the importance of the nucleophilicity of the anion, with halogens presenting the better results. Regarding the cation structure, it was possible to conclude that the bulkiness of the structure was the more important factor to have in consideration. Also the effects of pressure, temperature, type of solvent and catalyst concentration were studied and a high-pressure extraction process for an efficient product separation and recycling of the catalytic system was proposed. Finally, in the context of developing a green continuous flow process for CO2 conversion into cyclic carbonates, two different engineering approaches were investigated. On one hand a supported ionic liquid onto an alginate aerogel matrix was prepared, characterized and applied as catalytic system. On the other hand, a continuous flow process using a bulk ionic liquid phase as catalyst was carried out. Both processes allowed for cyclic carbonate production from a bio-based epoxide (limonene oxide) in the production of limonene carbonate, a 100% renewable cyclic carbonate. This thesis provides new opportunities for cyclic carbonate production from CO2 and epoxides in the context of sustainable processing.
[PT] O aquecimento global provocado principalmente pelo aumento das concentrações de gases de efeito estufa na atmosfera tornou-se numa das mais sérias preocupações em termos ambientais. Entre os principais gases responsáveis pelo efeito de estufa, temos o dióxido de carbono. Pelo facto de estar bastante disponível, de ser não inflamável, ter baixa toxicidade e devido a sua independência em relação a cadeia alimentar, o uso do CO2 como matéria-prima tem vindo a ganhar muita atenção quer do ponto de vista industrial e quer académico. O objetivo deste trabalho consiste no desenvolvimento de estratégias de intensificação do processo responsável pela produção de carbonatos cíclicos a partir da reação de epóxidos com CO2. Por sua vez, os carbonatos cíclicos produzidos tem várias aplicações, podem ser utilizados como eletrólitos nas baterias de lítio, como intermediários farmacêuticos e também como monómeros para a produção de polímeros. Pela primeira vez, complexos de zinco (II) de arilhidrazonas de -dicetonas combinados com líquidos iónicos foram utilizados como catalisadores na produção de carbonatos cíclicos. Diferentes famílias de aniões e catiões foram estudadas, com o objetivo de compreender o efeito destes grupos funcionais na selectividade e no rendimento final da reação. Os resultados confirmaram a importância da nucleofilicidade do anião, com os iões de halogénios a apresentar os melhores resultados. Preservando à estrutura de catião, foi possível concluir que o tamanho da estrutura era o fator mais importante a ter em consideração. O efeito da pressão, temperatura, tipo de solvente e catalisador foram alguns dos parâmetros estudados, adicionalmente um processo de extração a alta pressão foi proposto como forma eficiente de separação do produto final e reutilização do catalisador. Finalmente, com o objetivo de desenvolver uma tecnologia verde na conversão de CO2 em carbonatos cíclicos duas diferentes abordagens, em termos de engenharia, foram investigadas. Primeiro, foi preparado e devidamente caracterizado um catalisador suportado, composto por uma matriz de aerogéis de alginato, para posteriormente ser testado com sistema catalítico. Segundo, foi explorada a possibilidade de realizar esta reação em modo contínuo, utilizando com líquidos iónicos em “bulk” com catalisadores. Em ambos os processos foi possível a produção de carbonatos cíclicos a partir de um epóxido proveniente de recursos naturais (óxido de limoneno) produzindo assim carbonato de limoneno, um carbonato 100% bio-renovável. Esta tese fornece novas oportunidades para aumentar a produtividade do processo de produção de carbonatos cíclicos a partir do CO2.
Doctoral fellowship PD/BD/52497/2014, FCT/MEC (UID/QUI/50006/2013), ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER - 007265), project EXPL/QEQ-ERQ/2243/2013, project “Sun Storage – Harvesting and storage of solar energy”, reference POCI-01-0145-FEDER-016387, FCT (RECI/BBB-BQB/0230/2012) e AQUA-CO2NV ENE2014-53459-R.

Surface-charge regulated ionic transport phenomena in nano-pores and nano-channels have important applications in bio molecular analyses and power conversion involving NEMS. In such devises, the surface-to-volume ratio increases significantly. In nanofluidics, one characteristic is the overlapping of the electrical double layer (EDL) and the disappearance of the electrically neutral zone. The configuration to be considered is a finite length nano pore/channel connected by two reservoirs. Multi-dimensional analyses based on solutions of the Poisson-Nernst-Planck (PNP) equation were performed for the configuration in this study. Numerical solutions show that the ionic transport process in such a configuration depends strongly on the liquid-solid interface models used. These interface models usually serve as wall boundary conditions in multi-dimensional numerical analyses. Most current models were derived based on 1-D fully developed analyses. Issues regarding the extension of the surface chemical equilibrium model to multi-dimensional nanofluidics simulations involving overlapping EDLs were investigated and discussed in this paper.