Ionic liquids for efficient hydrogen sulfide and thiol scavenging

Functionalised pyridinium and ammonium ionic liquids bearing a Michael acceptor are shown to scavenge H₂S gas and various thiols, in most cases, without the aid of any added bases. Utilising the effective non-volatility of ionic liquids and ‘tagging’ malodourous substances to an ionic matrix renders them odourless.

Structuring reductive media containing protic ionic liquids and their application to the formation of metallic nanoparticles

Herein, we present a facile method for the formation of monodispersed metal nanoparticles (NPs) at room temperature from M^(III)Cl₃ (with M = Au, Ru, Mn, Fe or V) in different media based on N,N-dimethylformamide (DMF) or water solutions containing a protic ionic liquid (PIL), namely the octylammonium formate (denoted OAF) or the bis(2-ethyl-hexyl)ammonium formate (denoted BEHAF). These two PILs present different structures and redox-active structuring properties that influence their interactions with selected molecular compounds (DMF or water), as well as the shape and the size of formed metal NPs in these solutions. Herein, the physical properties, such as the thermal, transport and micellar properties, of investigated PIL solutions were firstly investigated in order to understand the relation between PILs structure and their properties in solutions with DMF or water. The formation of metal NPs in these solutions was then characterized by using UV–vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and dynamic light scattering (DLS) measurements. From our investigations, it appears that the PILs structure and their aggregation pathways in selected solvents affect strongly the formation, growths, the shape and the size of metal NPs. In fact by using this approach, the shape-/size-controlled metal NPs can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs.

Tunable gold nanoparticles shape and size in reductive and structuring media containing protic ionic liquids

Herein, a facile method was developed for preparing high concentration of monodispersed gold nanoparticles (NPs) at room temperature from gold(III) chloride by using different media based on N,N-dimethylformamide or water solutions containing a protic ionic liquid (PIL), namely, the octylammonium formate or the bis(2-ethyl-hexyl)ammonium formate, based on which both PILs were used as redox-active structuring media. The formation of gold NPs in these systems was then characterized using UV-visible spectroscopy, transmission electron microscopy, and dynamic light scattering. From these investigations, it appears that the structure and aggregation pathway of PILs in selected solvents affect strongly the formation, growth, the shape, and the size of gold NPs. In fact, by using this approach, the shape-/ size-controlled gold NPs (branched and spherical) can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs.

Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities

During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C₁OC_n][Sal]) with n = 3–11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K.

CO2 Capture in Wet and Dry Superbase Ionic Liquids

The solubility of carbon dioxide in five tetraalkylphosphonium superbase ionic liquids, namely the trihexyltetradecylphoshonium phenoxide, trihexyltetradecylphoshonium benzotriazolide, trihexyltetradecylphoshonium benzimidazolide, trihexyltetradecylphoshonium 1,2,3-triazolide, and trihexyltetradecylphoshonium 1,2,4-triazolide was studied experimentally under dry and wet conditions at 22 A degrees C and at atmospheric pressure, using a gravimetric saturation technique. The effects of anion structure and of the presence or absence of water in the solution on the carbon dioxide solubility were then deduced from the data. H-1 and C-13-NMR spectroscopy and ab initio calculations were also conducted to probe the interactions in these solutions, as carbon dioxide and water can compete in the ionic liquid structure during the absorption process. Additionally, the viscosity of selected superbase ionic liquids was measured under dry and wet conditions, in the presence or absence of CO2, to evaluate their practical application in carbon dioxide capture processes. Finally, the recyclability of the trihexyltetradecylphoshonium 1,2,4-triazolide under dry and wet conditions was determined to probe the ability of selected solvents to solubilize chemically a high concentration of carbon dioxide and then release it in a low energy demand process.

Mixtures of azepanium based ionic liquids and propylene carbonate as high voltage electrolytes for supercapacitors

This work provides a study of mixtures of the azepanium-based ionic liquid (IL) N-methyl, N-butyl-azepanium bis[(trifluoromethane) sulfonyl]imide (Azp₁₄TFSI) and propylene carbonate (PC) as electrolyte components in electrochemical double layer capacitors (EDLCs). The considered mixtures' properties were then compared to the properties of mixtures of N-butyl, N-methylpyrrolidinium bis[(trifluoromethane) sulfonyl]imide (Pyr₁₄TFSI) and PC in terms of viscosity, conductivity and electrochemical behavior. The mixtures' operative potentials were found to be comparable to each other, leading to operative voltages as high as 3.5 V, while retaining the low viscosities and high conductivities of PC based EDLC electrolytes.

Acoustic and Volumetric Properties of Diluted Solutions of Water in Ionic Liquids

Herein, we report the densities and speeds of sound in binary mixtures of three hydrophobic and one hydrophilic ionic liquids: 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [C4mim][NTf2], 1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, [C4mpyr][NTf2], 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [C3mim][NTf2] and 1-ethyl-3-methylimidazolium thiocyanate, [C2mim][SCN], with water at 298.15 K and 0.1 MPa. The concentration range of water, which encompassed relatively small values well below the saturation point, is often regarded as an impurity for hydrophobic ionic liquids. On the basis of experimental results the molar volume, adiabatic molar compressibility, partial molar volume and apparent molar volume, as well as, partial molar and apparent molar isentropic compressibility properties were then calculated. Interesting results are obtained using the solutions based on the hydrophilic [C2mim][SCN], since these mixtures are characterized by relatively low density and high values of speed of sound. Furthermore, the partial molar volumes and partial molar adiabatic compressibilities of water in solution with [C2mim][SCN] are the lowest among the investigated in mixtures with ionic liquids. However, in the case of the hydrophobic ionic liquid solutions, only small differences are observed for molar adiabatic compressibilities with the change of the cation structure, i.e. for water + [C4mim][NTf2] or + [C4mpyr][NTf2]. A more pronounced difference has been observed for the partial molar compressibility of water in solutions with these two ionic liquids.

One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

Dual functional ionic liquids as antimicrobials and plasticisers for medical grade PVCs

Two ionic liquids, 1-ethylpyridinium docusate (IL1) and tri-n-butyl(2-hydroxyethyl)phosphonium docusate (IL2), were designed and synthesized with the explicit intention of imparting a combination of plasticization and antimicrobial efficacy when incorporated into medical grade poly(vinyl chloride)s (PVCs). The glass transition (T-g) of PVC can be reduced by >20 degrees C on addition of 15 wt% IL2. Both IL1 and IL2 leached to varying extents from the base PVC resins rendering the surface of the PVCs hydrophilic. The antimicrobial activity of both ILs is related to the presence and concentration of both cationic and anionic component of the ILs leached from the PVC and inversely proportional to the extent of PVC gelation. Blends of the PVCs with IL1 displayed antibacterial activity against almost all Gram-positive bacteria tested, including coagulase-negative Staphylococci (CoNS) and methicillin-resistant Staphylococcus aureus (MRSA), but not with IL2 at low concentration in contrast to our previous study when high concentrations of IL2 were used. The more hydrophilic IL1 when added to PVC retards biofilm formation.

Thermochromism and switchable paramagnetism of cobalt(ii) in thiocyanate ionic liquids

Temperature-dependent switching of paramagnetism of a cobalt(ii) complex is observed in an ionic liquid solution. Paramagnetic and thermochromic switching occur simultaneously due to a reversible change in coordination. This reversible switching is possible in the ionic liquid solution, which enables mobility of thiocyanate anions by remaining mobile at low temperatures and acts as an anion reservoir.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Naphthenic acid extraction and speciation from Doba crude oil using carbonate-based ionic liquids

A number of tetraalkylammonium methylcarbonate and hydrogencarbonate based ionic liquids are shown to be capable of reacting with the naphthenic acids contained in Doba crude oil via a neutralisation reaction. Spectral studies show that the ionic liquids neutralisation mechanism involves the formation of an ionic liquid-naphthenate complex, liberating methanol and carbon dioxide. Extraction of the neutralised complex into a separate methanol phase and subsequent regeneration using aqueous carbonic acid results in ∼70% of the ionic liquid being recovered for recycle. Isolation of the naphthenic acids shows that these make up to 0.85 wt% of the crude oil. Speciation of the naphthenic acids shows a mixture of monocyclic, through to tetracyclic structures with carbon numbers in the range C₁₂-C₄₀.

Dissolution and processing of cellulose using ionic liquids, cellulose solution, and regenerating cellulose.

Cellulose is dissolved in an ionic liq. without derivatization, and is regenerated in a range of structural forms without requiring the use of harmful or volatile org. solvents. Cellulose soly. and the soln. properties can be controlled by the selection of the ionic liq. constituents, with small cations and halide or pseudohalide anions favoring soln.; dissoln. can be aided by irradn. An ionic liq., [C4mim]Cl, proved to be the best for dissolving cellulose. [on SciFinder(R)]