Protic Ionic Liquid as Reagent, Catalyst, and Solvent: 1-Methylimidazolium Thiocyanate.
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ABSTRACT:
SUBMITTER: Andreev IA
PROVIDER: S-EPMC8048580 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The development of the Li-ion battery Industry in a green way is crucial for human beings' future. Ionic liquids (ILs) are green cosolvents that could be applied in Li-ion battery electrolytes. A thermodynamic study has been carried out for a Li-ion electrolyte (propylene carbonate (PC) + LiCl and LiBr) in the presence of IL 1-alkyl-3-methylimidazolium thiocyanate [RMIM][SCN] (R = butyl, hexyl, and octyl). The studied thermodynamic properties were density, speed of sound, apparent molar volume, and compressibility. The effect of ILs in propylene carbonate (PC) has been investigated under atmospheric pressure at T = (288.15-318.15) K. Also, a microscopic approach using scaled particle theory has been implemented. The solvation effect of lithium halides, LiX (X = Cl-, Br-), on the volumetric and compressibility properties of the ILs has been studied at 298.15 K. The results show that [OMIM][SCN] has the strongest interactions with PC in the studied ILs and these interactions are more weakened with the addition of LiBr than LiCl. According to the partial molar compressibility results, the systems containing [OMIM][SCN] could be used under pressure more beneficially than other systems from the thermodynamic aspect of view.
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Project description:The large electrochemical and cycling stability of "water-in-salt" systems have rendered promising prospective electrolytes for batteries. The impact of addition of water on the properties of ionic liquids has already been addressed in several publications. In this contribution, we focus on the changes in the state of water. Therefore, we investigated the protic ionic liquid N-butyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide with varying water content at different temperatures with the aid of molecular dynamics simulations. It is revealed that at very low concentrations, the water is well dispersed and best characterized as shared solvent molecules. At higher concentrations, the water forms larger aggregates and is increasingly approaching a bulk-like state. While the librational and rotational dynamics of the water molecules become faster with increasing concentration, the translational dynamics are found to become slower. Further, all dynamics are found to be faster if the temperature increases. The trends of these findings are well in line with the experimental measured conductivities.
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Project description:We have carried out an ab initio molecular dynamics study on the sulfur dioxide (SO2) solvation in 1-ethyl-3-methylimidazolium thiocyanate for which we have observed that both cations and anions play an essential role in the solvation of SO2. Whereas, the anions tend to form a thiocyanate- and much less often an isothiocyanate-SO2 adduct, the cations create a "cage" around SO2 with those groups of atoms that donate weak interactions like the alkyl hydrogen atoms as well as the heavy atoms of the [Formula: see text]-system. Despite these similarities between the solvation of SO2 and CO2 in ionic liquids, an essential difference was observed with respect to the acidic protons. Whereas CO2 avoids accepting hydrogen bonds form the acidic hydrogen atoms of the cations, SO2 can from O(SO2)-H(cation) hydrogen bonds and thus together with the strong anion-adduct it actively integrates in the hydrogen bond network of this particular ionic liquid. The fact that SO2 acts in this way was termed a linker effect by us, because the SO2 can be situated between cation and anion operating as a linker between them. The particular contacts are the H(cation)[Formula: see text]O(SO2) hydrogen bond and a S(anion)-S(SO2) sulfur bridge. Clearly, this observation provides a possible explanation for the question of why the SO2 solubility in these ionic liquids is so high.
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Project description:We demonstrate a combined experimental and computational approach to probe the electronic structure and atomic environment of an ionic liquid, based on core level binding energies. The 1-butyl-3-methylimidazolium thiocyanate [C4C1Im][SCN] ionic liquid was studied using ab initio molecular dynamics, and results were compared against previously published and new experimental X-ray photoelectron spectroscopy (XPS) data. The long-held assumption that initial-state effects in XPS dominate the measured binding energies is proven correct, which validates the established premise that the ground state electronic structure of the ionic liquid can be inferred directly from XPS measurements. A regression model based upon site electrostatic potentials and intramolecular bond lengths is shown to account accurately for variations in core-level binding energies within the ionic liquid, demonstrating the important effect of long-range interactions on the core levels and throwing into question the validity of traditional single ion pair ionic liquid calculations for interpreting XPS data.
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Project description:An yttrium/europium oxide obtained by the processing of fluorescent lamp waste powder was separated into its individual elements by solvent extraction with two undiluted ionic liquids, trihexyl(tetradecyl)phosphonium thiocyanate, [C101][SCN], and tricaprylmethylammonium thiocyanate, [A336][SCN]. The best extraction performances were observed for [C101][SCN], by using an organic-to-aqueous volume ratio of 1/10 and four counter-current extraction stages. The loaded organic phase was afterwards subjected to scrubbing with a solution of 3 mol L-1 CaCl2 + 0.8 mol L-1 NH4SCN to remove the co-extracted europium. Yttrium was quantitatively stripped from the scrubbed organic phase by deionized water. Yttrium and europium were finally recovered as hydroxides by precipitation with ammonia and then calcined to the corresponding oxides. The conditions thus defined for an efficient yttrium/europium separation from synthetic chloride solutions were afterwards tested on a leachate obtained from the dissolution of a real mixed oxide. The purity of Y2O3 with respect to the rare-earth content was 98.2%; the purity of Eu2O3 with respect to calcium was 98.7%.
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Project description:Solvents that stabilize protein structures can improve and expand their biochemical applications, particularly with the growing interest in biocatalytic-based processes. Aiming to select novel solvents for protein stabilization, we explored the effect of alkylammonium nitrate protic ionic liquids (PILs)-water mixtures with increasing cation alkyl chain length on lysozyme conformational stability. Four PILs were studied, that is, ethylammonium nitrate (EAN), butylammonium nitrate (BAN), hexylammonium nitrate (HAN), and octylammonium nitrate (OAN). The surface tension, viscosity, and density of PIL-water mixtures at low to high concentrations were firstly determined, which showed that an increasing cation alkyl chain length caused a decrease in the surface tension and density as well as an increase in viscosity for all PIL solutions. Small-angle X-ray scattering (SAXS) was used to investigate the liquid nanostructure of the PIL solutions, as well as the overall size, conformational flexibility and changes to lysozyme structure. The concentrated PILs with longer alkyl chain lengths, i.e., over 10 mol% butyl-, 5 mol% hexyl- and 1 mol% octylammonium cations, possessed liquid nanostructures. This detrimentally interfered with solvent subtraction, and the more structured PIL solutions prevented quantitative SAXS analysis of lysozyme structure. The radius of gyration (Rg) of lysozyme in the less structured aqueous PIL solutions showed little change with up to 10 mol% of PIL. Kratky plots, SREFLEX models, and FTIR data showed that the protein conformation was maintained at a low PIL concentration of 1 mol% and lower when compared with the buffer solution. However, 50 mol% EAN and 5 mol% HAN significantly increased the Rg of lysozyme, indicating unfolding and aggregation of lysozyme. The hydrophobic interaction and liquid nanostructure resulting from the increased cation alkyl chain length in HAN likely becomes critical. The impact of HAN and OAN, particularly at high concentrations, on lysozyme structure was further revealed by FTIR. This work highlights the negative effect of a long alkyl chain length and high concentration of PILs on lysozyme structural stability.
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Project description:The structure and properties of different biopolymer composites based on chitosan and chitosan/carboxymethyl cellulose (CMC) are governed by multiple structure-property relationships associated with different phase interactions. Plasticization of these matrices with ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) played a dominant role, increasing the mobility of biopolymer chains as well as ions and associated dipoles but reducing biopolymer chain interactions, crystallinity, and thermal stability. These structural changes led to higher matrix ionic conductivity, shorter electrical relaxation time, and greater matrix ductility. The inclusion of graphene oxide (GO) and reduced GO (rGO) also influenced the structure and properties of these bionanocomposites by disrupting the biopolymer hydrogen bonding and/or polyelectrolyte complexation (PEC) and interacting with [C2mim][OAc]. The impact of GO/rGO was more evident for 20 wt % [C2mim][OAc], such as increased crystallinity and thermal stability of chitosan. PEC was hindered with excess (40 wt %) [C2mim][OAc] added and further hindered again when rGO was included. This study shows that the structure and properties of bionanocomposites are not just determined by the surface chemistry of GO/rGO but can also be influenced by multiple interactions involving plasticizers such as ILs and additional biopolymers.
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Project description:The dynamics of excess protons in the protic ionic liquid (PIL) ethylammonium formate (EAF) have been investigated from femtoseconds to microseconds using visible pump mid-infrared probe spectroscopy. The pH jump following the visible photoexcitation of a photoacid (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt, HPTS) results in proton transfer to the formate of the EAF. The proton transfer predominantly (∼70%) occurs over picoseconds through a preformed hydrogen-bonded tight complex between HPTS and EAF. We investigate the longer-range and longer-time-scale proton-transport processes in the PIL by obtaining the ground-state conjugate base (RO-) dynamics from the congested transient-infrared spectra. The spectral kinetics indicate that the protons diffuse only a few solvent shells from the parent photoacid before recombining with RO-. A kinetic isotope effect of nearly unity (kH/kD ≈ 1) suggests vehicular transfer and the transport of excess protons in this PIL. Our findings provide comprehensive insight into the complete photoprotolytic cycle of excess protons in a PIL.
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Project description:Confinement effects for the magnetoresponsive ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate(III), [C2mim]FeCl4, are explored from thermal, spectroscopic, and magnetic points of view. Placing the ionic liquid inside SBA-15 mesoporous silica produces a significant impact on the material's response to temperature, pressure, and magnetic fields. Isobaric thermal experiments show melting point reductions that depend on the pore diameter of the mesopores. The confinement-induced reductions in phase transition temperature follow the Gibbs-Thomson equation if a 1.60 nm non-freezable interfacial layer is postulated to exist along the pore wall. Isothermal pressure-dependent infrared spectroscopy reveals a similar modification to phase transition pressures, with the confined ionic liquid requiring higher pressures to trigger phase transformation than the unconfined system. Confinement also impedes ion transport as activation energies are elevated when the ionic liquid is placed inside the mesopores. Finally, the antiferromagnetic ordering that characterizes unconfined [C2mim]FeCl4 is suppressed when the ionic liquid is confined in 5.39-nm pores. Thus, confinement provides another avenue for manipulating the magnetic properties of this compound.
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Project description:Lignin can be considered an essential under-exploited polymer from lignocellulosic biomass representing a key for a profitable biorefinery. One method of lignin valorization could be the improvement of physico-chemical properties by esterification to enhance miscibility in apolar polyolefin matrices, thereby helping the production of bio-based composites. The present work describes for the first time a succeeded chemical esterification of industrial lignins with maleic anhydride in an acidic ionic liquid: 1-butyl-3-methyl imidazolium hydrogen sulfate without additional catalyst. This efficient strategy was applied to four industrial lignins: two softwood Kraft lignins (Indulin AT, Wayagamack), one hardwood Kraft lignin (Windsor), and one softwood organosolv lignin (Lignol), distinct in origin, extraction process and thus chemical structure. The chemical, structural, and thermal properties of modified lignins were characterized by 31P nuclear magnetic resonance, infrared spectroscopy and thermal analyses, then compared to those of unmodified lignins. After 4 h of reaction, between 30 to 52% of the constitutive hydroxyls were esterified depending on the type of lignin sample. The regioselectivity of the reaction was demonstrated to be preferentially orientated toward aliphatic hydroxyls for three out of four lignins (66.6, 65.5, and 83.6% for Indulin AT, Windsor and Lignol, respectively, vs. 51.7% for Wayagamack). The origin and the extraction process of the polymer would thus influence the efficiency and the regioselectivity of this reaction. Finally, we demonstrated that the covalent grafting of maleyl chain on lignins did not significantly affect thermal stability and increased significantly the solubility in polar and protic solvent probably due to additional exposed carboxylic groups resulted from mono-acylation independently of H/G/S ratio. Blending with polyolefins could then be considered in regard of compatibility with the obtained physico-chemical properties.
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