Ionic Liquid Stabilizes Olefin Facilitated Transport Membranes Against Reduction.

Separation of olefins from their paraffin analogs relies on energy-intensive cryogenic distillation. Facilitated transport-based membranes that reversibly and selectively bind olefins, but not paraffins, could save considerable amounts of energy. However, the chemical instability of the silver ion olefin-binding carriers in such membranes has been a longstanding roadblock for this approach. We discovered long-term carrier stability against extended exposure to hydrogen, a common contaminant in such streams. Based on UV/Vis absorption and Raman spectroscopy, along with XRD analysis results, certain ionic liquids solubilize silver ions, and anion aggregates surrounding the silver ion carriers greatly attenuate their reduction by hydrogen. Here, we report the stability of olefin/paraffin separation properties under continuous exposure to high pressure hydrogen, which addresses a critical technical roadblock in membrane-based olefin/paraffin separation.

Investigation of Multilayered Structures of Ionic Liquids on Graphite and Platinum Using Atomic Force Microscopy and Molecular Simulations.

The molecular-level orientation and structure of ionic liquids (ILs) at liquid-solid interfaces are significantly different than in the bulk. The interfacial ordering influences both IL properties, such as dielectric constants and viscosity, and their efficacy in devices, such as fuel cells and electrical capacitors. Here, we report the layered structures of four ILs on unbiased, highly ordered pyrolytic graphite (HOPG) and Pt(111) surfaces, as determined by atomic force microscopy. The ILs investigated are 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]), 1-ethyl-3-methylimidazolium perfluorobutylsulfonate ([emim][C4F9SO3]), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene bis(trifluoromethylsulfonyl)imide ([MTBD][Tf2N]), and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene perfluorobutylsulfonate ([MTBD][C4F9SO3]). Molecular dynamics simulations provide complementary information on the position and orientation of the ions. These ILs form a cation layer at the IL-solid interface, followed by a layer of anions. [Emim]+ and [MTBD]+ have similar orientations at the surface, but [MTBD]+ forms a thinner layer compared to [emim]+ on both HOPG and Pt(111). In addition, [Tf2N]- shows stronger interactions with Pt(111) surfaces than [C4F9SO3]-.

In situ nanoscale evaluation of pressure-induced changes in structural morphology of phosphonium phosphate ionic liquid at single-asperity contacts.

In this work, we perform atomic force microscopy (AFM) experiments to evaluate in situ the dependence of the structural morphology of trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate ([P6,6,6,14][DEHP]) ionic liquid (IL) on applied pressure. The experimental results obtained upon sliding a diamond-like-carbon-coated silicon AFM tip on mechanically polished steel at an applied pressure up to 5.5 ± 0.3 GPa indicate a structural transition of confined [P6,6,6,14][DEHP] molecules. This pressure-induced morphological change of [P6,6,6,14][DEHP] IL leads to the generation of a lubricious, solid-like interfacial layer, whose growth rate increases with applied pressure and temperature. The structural variation of [P6,6,6,14][DEHP] IL is proposed to derive from the well-ordered layering of the polar groups of ions separated by the apolar tails. These results not only shed new light on the structural organization of phosphonium-based ILs under elevated pressure, but also provide novel insights into the normal pressure-dependent lubrication mechanisms of ILs in general.

Cation-Anion and Anion-CO2 Interactions in Triethyl(octyl)phosphonium Ionic Liquids with Aprotic Heterocyclic Anions (AHAs).

Ionic liquids with aprotic heterocyclic anions (AHAs) have been developed for postcombustion CO2 capture applications. The anions of AHA ILs play a significant role in tuning anion-CO2 complexation. In addition, AHAs are able to trigger the abstraction of acidic protons located at the α position of phosphonium cations by forming hydrogen bonds between cations and anions, eventually leading to cation-driven CO2 complexation. Here we investigate the role of the anion in cation-anion hydrogen bonding and ylide formation. Using CO2 uptake measurements, 31P nuclear magnetic resonance (NMR), attenuated total reflection-Fourier transform infrared (ATR-FTIR) deuterium exchange equilibrium and rates, two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY), and density functional theory calculations, we show that the key is the proximity of the negatively charged nitrogen atoms on the anion to the α protons, which is governed not just by anion basicity but by sterics. Thus, we show that triethyl(octyl)phosphonium 3-methyl-5-trifluoromethylpyrazolide is much more effective in hydrogen-bonding with and deprotonating the cation than the equivalent [P2228] ILs with more basic 2-cyanopyrrolide and 3-trifluoromethylpyrazolide anions.

Protic Imidazolium Cation-Based Ionic Liquids Show Unexpected Interfacial Properties.

Virtually, every investigation and application of ionic liquids (ILs) involves gas-liquid, liquid-liquid, and liquid-solid interactions. Therefore, understanding the behavior of ILs at those interfaces is critical. In this work, we studied the interfacial properties of protic and aprotic ILs with N-alkylimidazolium and 1-alkyl-3-methylimidazolium as cations and bis(trifluoromethylsulfonyl)imide, methanesulfonate, and trifluoromethanesulfonate as anions. The surface tension of these ILs is measured with the pendant drop method in a temperature range of 293.15-343.15 K and at atmospheric pressure. The contact angle measurements are performed at 293.15 K on three solid substrates: polytetrafluoroethylene, glassy carbon, and platinum. Dispersive and nondispersive components of the IL surface energy are determined from the experimental data using Fowkes theory. The most interesting result is that the protic ILs have lower surface tension and smaller contact angles than the equivalent aprotic ILs, despite the presence of high charge density on the proton associated with one of the nitrogens of the cation. Higher charge density on the anion results in a higher surface tension, and decreasing surface tension and contact angles are observed for increasing alkyl chain length on the cation.

6,7-Di-hydro-5H-pyrrolo-[1,2-a]imidazole.

The crystal structure of 6,7-di-hydro-5H-pyrrolo-[1,2-a]imidazole, C6H8N2, at 100 K has monoclinic (P21/n) symmetry. The mol-ecule adopts an envelope conformation of the pyrrolidine ring, which might help for the relief torsion tension. The crystal cohesion is achieved by C-H⋯N hydrogen bonds. Inter-estingly, this fused ring system provides protection of the α-C atom (attached to the non-bridging N atom of the imidazole ring), which provides stability that is of inter-est with respect to electrochemical properties as electrolytes for fuel cells and batteries, and electrodeposition.

Cation-Anion Interactions in 1-Ethyl-3-methylimidazolium-Based Ionic Liquids with Aprotic Heterocyclic Anions (AHAs).

Ionic liquids with aprotic heterocyclic anions (AHAs) have been developed for CO2 capture but have been considered for other applications as well. Previously, we have shown that AHA ILs, where the only site for reaction with CO2 is the anion, the CO2 capacity correlates with anion basicity. Moreover, we have shown that 1-ethyl-3-methylimidazolium ([Emim]+)AHA ILs can react with CO2 in two ways. The first is with the anion to form a carbamate. The second is by reaction of the deprotonated C2 of the imidazolium cation to form a carboxylate. Here we show that the amount of carboxylate formed when [Emim]+ AHA ILs are exposed to CO2 is not proportional to the anion basicity, contrary to expectations. Rather, it is roughly the same for all AHA ILs investigated, as long as the anion is able to readily deprotonate the C2. Moreover, the strength of the hydrogen bond between C2-H and the anion is not proportional to the anion basicity, once again contrary to expectations. In addition, we discovered that deuterium exchange occurs not only with the acidic proton on the C2 of the cation but also with the less acidic C4 and C5 protons of the imidazolium cation, when the anions are sufficiently basic. These conclusions were reached based on quantification of cation-CO2 and anion-CO2 complex formation, IR spectra, 1H NMR chemical shifts, and deuterium exchange equilibrium and kinetics.

Encapsulation of Ionic Liquids with an Aprotic Heterocyclic Anion (AHA-IL) for CO2 Capture: Preserving the Favorable Thermodynamics and Enhancing the Kinetics of Absorption.

The performance of an ionic liquid with an aprotic heterocyclic anion (AHA-IL), trihexyl(tetradecyl)phosphonium 2-cyanopyrrolide ([P66614][2-CNPyr]), for CO2 capture has been evaluated considering both the thermodynamics and the kinetics of the phenomena. Absorption gravimetric measurements of the gas-liquid equilibrium isotherms of CO2-AHA-IL systems were carried out from 298 to 333 K and at pressures up to 15 bar, analyzing the role of both chemical and physical absorption phenomena in the overall CO2 solubility in the AHA-IL, as has been done previously. In addition, the kinetics of the CO2 chemical absorption process was evaluated by in situ Fourier transform infrared spectroscopy-attenuated total reflection, following the characteristic vibrational signals of the reactants and products over the reaction time. A chemical absorption model was used to describe the time-dependent concentration of species involved in the reactive absorption, obtaining kinetic parameters (such as chemical reaction kinetic constants and diffusion coefficients) as a function of temperatures and pressures. As expected, the results demonstrate that the CO2 absorption rate is mass-transfer-controlled because of the relatively high viscosity of AHA-IL. The AHA-IL was encapsulated in a porous carbon sphere (Encapsulated Ionic Liquid, ENIL) to improve the kinetic performance of the AHA-IL for CO2 capture. The newly synthesized AHA-ENIL material was evaluated as a CO2 sorbent with gravimetric absorption measurements. AHA-ENIL systems preserve the good CO2 absorption capacity of the AHA-IL but drastically enhance the CO2 absorption rate because of the increased gas-liquid surface contact area achieved by solvent encapsulation.

Micellization and Single-Particle Encapsulation with Dimethylammoniopropyl Sulfobetaines.

Sulfobetaines (SBs) are a class of zwitterionic surfactants with a reputation for enhancing colloidal stability at high salt concentrations. Here, we present a systematic study on the self-assembly of SB amphiphiles (sultaines or hydroxysultaines) in aqueous solutions, as a function of chain length and composition, ionic strength, and in the presence of alkanethiol-coated Au nanoparticles (GNPs). The diameters of the micelles assembled from SB and amidosulfobetaine (ASB) generally increase monotonically with chain length, although ASB micelles are smaller relative to alkyl SB micelles with similarly sized tailgroups, and oleyl sulfobetaine (OSB) micelles are slightly larger. SB amphiphiles can stabilize alkanethiol-coated GNPs in physiologically relevant buffers at concentrations well below their CMC, with size increases corresponding to single-particle encapsulation. SB-encapsulated GNPs were prepared by three different methods with SB:GNP weight ratios of 10:1, followed by dispersion in water or 1 M NaCl. The low hydrodynamic size of the SB micelles and SB-coated NPs is within the range needed for efficient renal clearance.

Liquid Structure of CO2-Reactive Aprotic Heterocyclic Anion Ionic Liquids from X-ray Scattering and Molecular Dynamics.

A combination of X-ray scattering experiments and molecular dynamics simulations were conducted to investigate the structure of ionic liquids (ILs) which chemically bind CO2. The structure functions were measured and computed for four different ILs consisting of two different phosphonium cations, triethyloctylphosphonium ([P2228]+) and trihexyltetradecylphosphonium ([P66614]+), paired with two different aprotic heterocyclic anions which chemically react with CO2, 2-cyanopyrrolide, and 1,2,4-triazolide. Simulations were able to reproduce the experimental structure functions, and by deconstructing the simulated structure functions, further information on the liquid structure was obtained. All structure functions of the ILs studied had three primary features which have been seen before in other ILs: a prepeak near 0.3-0.4 Å-1 corresponding to polar/nonpolar domain alternation, a charge alternation peak near 0.8 Å-1, and a peak near 1.5 Å-1 due to interactions of adjacent molecules. The liquid structure functions were only mildly sensitive to the specific anion and whether or not they were reacted with CO2. Upon reacting with CO2, small changes were observed in the structure functions of the [P2228]+ ILs, whereas virtually no change was observed upon reacting with CO2 in the corresponding [P66614]+ ILs. When the [P2228]+ cation was replaced with the [P66614]+ cation, there was a significant increase in the intensities of the prepeak and adjacency interaction peak. While many of the liquid structure functions are similar, the actual liquid structures differ as demonstrated by computed spatial distribution functions.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation.

A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications.

CO2 Chemistry of Phenolate-Based Ionic Liquids.

We synthesized ionic liquids (ILs) comprising an alkylphosphonium cation paired with phenolate, 4-nitrophenolate, and 4-methoxyphenolate anions that span a wide range of predicted reaction enthalpies with CO2. Each phenolate-based IL was characterized by spectroscopic techniques, and their physical properties (viscosity, conductivity, and CO2 solubility) were determined. We use the computational quantum chemical approach paired with experimental results to reveal the reaction mechanism of CO2 with phenolate ILs. Model chemistry shows that the oxygen atom of phenolate associates strongly with phosphonium cations and is able to deprotonate the cation to form an ylide with an affordable activation barrier. The ATR-FTIR and (31)P NMR spectra indicate that the phosphonium ylide formation and its reaction with CO2 are predominantly responsible for the observed CO2 uptake rather than direct anion-CO2 interaction.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room-Temperature Ionic Liquids. 1. Variation of Anionic Species.

A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications.

Sulfoform generation from an orthogonally protected disaccharide.

An orthogonally protected disaccharide (GlcN(α1→4)Glc) with a ß-linked 2'-aminoethyl linker was used to generate a series of sulfated derivatives (sulfoforms), with a 6-O-sulfate on the glucose residue and one or more sulfate esters on the terminal glucosamine. Deprotection and sulfonation steps were performed in solution and in variable order, with isolated yields of 36-54% (85-90% per operation) after HPLC purification. The modular deprotection-sulfonation sequences can be performed with efficient recovery of the polysulfate products, and avoids complications associated with heterogeneous reactivity in solid-phase synthesis.