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Sample records for room-temperature ionic liquid

  1. Structure of room temperature ionic liquids.

    PubMed

    Yethiraj, Arun

    2016-10-19

    The structure of room temperature ionic liquids is studied using molecular dynamics simulations and integral equation theory. Three ionic liquids 1-alkyl-3-methylimidazolium hexfluorophosphate, [C n MIM] [PF6], for n  =  1, 4, and 8, are studied using a united atom model of the ions. The primary interest is a study of the pair correlation functions and a test of the reference interaction site model theory. There is liquid-like ordering in the liquid that arises from electrostatic attractions and steric packing considerations. The theory is not in quantitative agreement with the simulation results and underestimates the degree of liquid-like order. A pre-peak in the static structure factor is seen in both simulations and theory, suggesting that this is a geometric effect arising from a packing of the alkyl chains. PMID:27546807

  2. Water in Room Temperature Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Fayer, Michael

    2014-03-01

    Room temperature ionic liquids (or RTILs, salts with a melting point below 25 °C) have become a subject of intense study over the last several decades. Currently, RTIL application research includes synthesis, batteries, solar cells, crystallization, drug delivery, and optics. RTILs are often composed of an inorganic anion paired with an asymmetric organic cation which contains one or more pendant alkyl chains. The asymmetry of the cation frustrates crystallization, causing the salt's melting point to drop significantly. In general, RTILs are very hygroscopic, and therefore, it is of interest to examine the influence of water on RTIL structure and dynamics. In addition, in contrast to normal aqueous salt solutions, which crystallize at low water concentration, in an RTIL it is possible to examine isolated water molecules interacting with ions but not with other water molecules. Here, optical heterodyne-detected optical Kerr effect (OHD-OKE) measurements of orientational relaxation on a series of 1-alkyl-3-methylimidazolium tetrafluoroborate RTILs as a function of chain length and water concentration are presented. The addition of water to the longer alkyl chain RTILs causes the emergence of a long time bi-exponential orientational anisotropy decay. Such decays have not been seen previously in OHD-OKE experiments on any type of liquid and are analyzed here using a wobbling-in-a-cone model. The orientational relaxation is not hydrodynamic, with the slowest relaxation component becoming slower as the viscosity decreases for the longest chain, highest water content samples. The dynamics of isolated D2O molecules in 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) were examined using two dimensional infrared (2D IR) vibrational echo spectroscopy. Spectral diffusion and incoherent and coherent transfer of excitation between the symmetric and antisymmetric modes are examined. The coherent transfer experiments are used to address the nature of inhomogeneous

  3. Room-Temperature Ionic Liquids for Electrochemical Capacitors

    NASA Technical Reports Server (NTRS)

    Fireman, Heather; Yowell, Leonard; Moloney, Padraig G.; Arepalli, Sivaram; Nikolaev, P.; Huffman, C.; Ready, Jud; Higgins, C.D.; Turano, S. P.; Kohl, P.A.; Kim, K.

    2009-01-01

    A document discusses room-temperature ionic liquids (RTILs) used as electrolytes in carbon-nanotube-based, electrochemical, double-layer capacitors. Unlike the previous electrolyte (EtNB4 in acetonitrile), the RTIL used here does not produce cyanide upon thermal decomposition and does not have a moisture sensitivity.

  4. Dynamics and structure of room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Fayer, Michael D.

    2014-11-01

    Room temperature ionic liquids (RTIL) are intrinsically interesting because they simultaneously have properties that are similar to organic liquids and liquid salts. In addition, RTILs are increasingly being considered for and used in technological applications. RTILs are usually composed of an organic cation and an inorganic anion. The organic cation, such as imidazolium, has alkyl chains of various lengths. The disorder in the liquid produced by the presence of the alkyl groups lowers the temperature for crystallization below room temperature and can also result in supercooling and glass formation rather than crystallization. The presence of the alkyl moieties also results in a segregation of the liquid into ionic and organic regions. In this article, experiments are presented that address the relationship between RTIL dynamics and structure. Time resolved fluorescence anisotropy measurements were employed to study the local environments in the organic and ionic regions of RTILs using a nonpolar chromophore that locates in the organic regions and an ionic chromophore that locates in the ionic regions. In the alkyl regions, the in plane and out of plane orientational friction coefficients change in different manners as the alkyl chains get longer. Both friction coefficients converge toward those of a long chain length hydrocarbon as the RTIL chains increase in length, which demonstrates that for sufficiently long alkyl chains the RTIL organic regions have properties similar to a hydrocarbon. However, putting Li+ in the ionic regions changes the friction coefficients in the alkyl regions, which demonstrates that changes of the ion structural organization influences the organization of the alkyl chains. Optical heterodyne detected optical Kerr effect (OHD-OKE) experiments were used to examine the orientational relaxation dynamics of RTILs over times scales of a hundred femtoseconds to a hundred nanoseconds. Detailed temperature dependent studies in the liquid and

  5. Contracting cardiomyocytes in hydrophobic room-temperature ionic liquid

    SciTech Connect

    Hoshino, Takayuki; Fujita, Kyoko; Higashi, Ayako; Sakiyama, Keiko; Ohno, Hiroyuki; Morishima, Keisuke

    2012-10-19

    Highlights: Black-Right-Pointing-Pointer Biocompatible room-temperature ionic liquid was applied on beating cardiomyocyte. Black-Right-Pointing-Pointer The lifetime of beating cardiomyocytes was depended on anion functional group. Black-Right-Pointing-Pointer A longer lifetime was recorded for no functional group on alkyl chain on their anion. Black-Right-Pointing-Pointer Amino group on alkyl chain and fluorine in anion induced fatal condition changes. Black-Right-Pointing-Pointer We reported liquid electrolyte interface to stimulate cardiomyocytes. -- Abstract: Room-temperature ionic liquids (RTILs) are drawing attention as a new class of nonaqueous solvents to replace organic and aqueous solvents for chemical processes in the liquid phase at room temperature. The RTILs are notable for their characteristics of nonvolatility, extremely low vapor pressure, electric conductivity, and incombustibility. These distinguished properties of RTILs have brought attention to them in applications with biological cells and tissue in vacuum environment for scanning electron microscopy, and in microfluidic devices for micro-total analysis system (micro-TAS). Habitable RTILs could increase capability of nonaqueous micro-TAS for living cells. Some RTILs seemed to have the capability to replace water in biological applications. However, these RTILs had been applied to just supplemental additives for biocompatible test, to fixed cells as a substitute for an aqueous solution, and to simple molecules. None of RTILs in which directly soaks a living cell culture. Therefore, we demonstrated the design of RTILs for a living cell culture and a liquid electrolyte to stimulate contracting cardiomyocytes using the RTILs. We assessed the effect of RTILs on the cardiomyocytes using the beating lifetime to compare the applicability of RTILs for biological applications. Frequent spontaneous contractions of cardiomyocytes were confirmed in amino acid anion RTILs [P{sub 8,8,8,8}][Leu] and [P{sub 8

  6. Microstructure of room temperature ionic liquids at stepped graphite electrodes

    SciTech Connect

    Feng, Guang; Li, Song; Zhao, Wei; Cummings, Peter T.

    2015-07-14

    Molecular dynamics simulations of room temperature ionic liquid (RTIL) [emim][TFSI] at stepped graphite electrodes were performed to investigate the influence of the thickness of the electrode surface step on the microstructure of interfacial RTILs. A strong correlation was observed between the interfacial RTIL structure and the step thickness in electrode surface as well as the ion size. Specifically, when the step thickness is commensurate with ion size, the interfacial layering of cation/anion is more evident; whereas, the layering tends to be less defined when the step thickness is close to the half of ion size. Furthermore, two-dimensional microstructure of ion layers exhibits different patterns and alignments of counter-ion/co-ion lattice at neutral and charged electrodes. As the cation/anion layering could impose considerable effects on ion diffusion, the detailed information of interfacial RTILs at stepped graphite presented here would help to understand the molecular mechanism of RTIL-electrode interfaces in supercapacitors.

  7. Phosphonium chloromercurate room temperature ionic liquids of variable composition.

    PubMed

    Metlen, Andreas; Mallick, Bert; Murphy, Richard W; Mudring, Anja-Verena; Rogers, Robin D

    2013-12-16

    The system trihexyl(tetradecyl)phosphonium ([P66614]Cl)/mercury chloride (HgCl2) has been investigated by varying the stoichiometric ratios from 4:1 to 1:2 (25, 50, 75, 100, 150, and 200 mol % HgCl2). All investigated compositions turn out to give rise to ionic liquids (ILs) at room temperature. The prepared ionic liquids offer the possibility to study the structurally and compositionally versatile chloromercurates in a liquid state at low temperatures in the absence of solvents. [P66614]2[HgCl4] is a simple IL with one discrete type of anion, while [P66614]{HgCl3} (with {} indicating a polynuclear arrangement) is an ionic liquid with a variety of polyanionic species, with [Hg2Cl6](2-) apparently being the predominant building block. [P66614]2[Hg3Cl8] and [P66614][Hg2Cl5] appear to be ILs at ambient conditions but lose HgCl2 when heated in a vacuum. For the liquids with the compositions 4:1 and 4:3, more than two discrete ions can be evidenced, namely, [P66614](+), [HgCl4](2-), and Cl(-) and [P66614](+), [HgCl4](2-), and the polynuclear {HgCl3}(-), respectively. The different stoichiometric compositions were characterized by (199)Hg NMR, Raman- and UV-vis spectroscopy, and cyclic voltammetry, among other techniques, and their densities and viscosities were determined. The [P66614]Cl/HgCl2 system shows similarities to the well-known chloroaluminate ILs (e.g., decrease in viscosity with increasing metal content after addition of more than 0.5 mol of HgCl2/mol [P66614]Cl, increasing density with increasing metal content, and the likely formation of polynuclear/polymeric/polyanionic species) but offer the advantage that they are air and water stable. PMID:24274831

  8. Contracting cardiomyocytes in hydrophobic room-temperature ionic liquid.

    PubMed

    Hoshino, Takayuki; Fujita, Kyoko; Higashi, Ayako; Sakiyama, Keiko; Ohno, Hiroyuki; Morishima, Keisuke

    2012-10-19

    Room-temperature ionic liquids (RTILs) are drawing attention as a new class of nonaqueous solvents to replace organic and aqueous solvents for chemical processes in the liquid phase at room temperature. The RTILs are notable for their characteristics of nonvolatility, extremely low vapor pressure, electric conductivity, and incombustibility. These distinguished properties of RTILs have brought attention to them in applications with biological cells and tissue in vacuum environment for scanning electron microscopy, and in microfluidic devices for micro-total analysis system (micro-TAS). Habitable RTILs could increase capability of nonaqueous micro-TAS for living cells. Some RTILs seemed to have the capability to replace water in biological applications. However, these RTILs had been applied to just supplemental additives for biocompatible test, to fixed cells as a substitute for an aqueous solution, and to simple molecules. None of RTILs in which directly soaks a living cell culture. Therefore, we demonstrated the design of RTILs for a living cell culture and a liquid electrolyte to stimulate contracting cardiomyocytes using the RTILs. We assessed the effect of RTILs on the cardiomyocytes using the beating lifetime to compare the applicability of RTILs for biological applications. Frequent spontaneous contractions of cardiomyocytes were confirmed in amino acid anion RTILs [P(8,8,8,8)][Leu] and [P(8,8,8,8)][Ala], phosphoric acid derivatives [P(8,8,8,8)][MeO(H)PO(2)], and [P(8,8,8,8)][C(7)CO(2)]. The anion type of RTILs had influence on applicable characteristics for the contracting cardiomyocyte. This result suggested the possibility for biocompatible design of hydrophobic group RTILs to achieve biological applications with living cells. PMID:23000154

  9. Synthesis of tin nanocrystals in room temperature ionic liquids.

    PubMed

    Le Vot, Steven; Dambournet, Damien; Groult, Henri; Ngo, Anh-tu; Petit, Christophe; Rizzi, Cécile; Salzemann, Caroline; Sirieix-Plenet, Juliette; Borkiewicz, Olaf J; Raymundo-Piñero, Encarnación; Gaillon, Laurent

    2014-12-28

    The aim of this work was to investigate the synthesis of tin nanoparticles (NPs) or tin/carbon composites, in room temperature ionic liquids (RTILs), that could be used as structured anode materials for Li-ion batteries. An innovative route for the synthesis of Sn nanoparticles in such media is successfully developed. Compositions, structures, sizes and morphologies of NPs were characterized by high-energy X-ray diffraction (HEXRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). Our findings indicated that (i) metallic tetragonal β-Sn was obtained and (ii) the particle size could be tailored by tuning the nature of the RTILs, leading to nano-sized spherical particles with a diameter ranging from 3 to 10 nm depending on synthesis conditions. In order to investigate carbon composite materials for Li-ion batteries, Sn nanoparticles were successfully deposited on the surface of multi-wall carbon nanotubes (MWCNT). Moreover, electrochemical properties have been studied in relation to a structural study of the nanocomposites. The poor electrochemical performances as a negative electrode in Li-ion batteries is due to a significant amount of RTIL trapped within the pores of the nanotubes as revealed by XPS investigations. This dramatically affected the gravimetric capacity of the composites and limited the diffusion of lithium. The findings of this work however offer valuable insights into the exciting possibilities for synthesis of novel nano-sized particles and/or alloys (e.g. Sn-Cu, Sn-Co, Sn-Ni, etc.) and the importance of carbon morphology in metal pulverization during the alloying/dealloying process as well as prevention of ionic liquid trapping. PMID:25352309

  10. Mesophases in nearly 2D room-temperature ionic liquids.

    PubMed

    Manini, N; Cesaratto, M; Del Pópolo, M G; Ballone, P

    2009-11-26

    Computer simulations of (i) a [C(12)mim][Tf(2)N] film of nanometric thickness squeezed at kbar pressure by a piecewise parabolic confining potential reveal a mesoscopic in-plane density and composition modulation reminiscent of mesophases seen in 3D samples of the same room-temperature ionic liquid (RTIL). Near 2D confinement, enforced by a high normal load, as well as relatively long aliphatic chains are strictly required for the mesophase formation, as confirmed by computations for two related systems made of (ii) the same [C(12)mim][Tf(2)N] adsorbed at a neutral solid surface and (iii) a shorter-chain RTIL ([C(4)mim][Tf(2)N]) trapped in the potential well of part i. No in-plane modulation is seen for ii and iii. In case ii, the optimal arrangement of charge and neutral tails is achieved by layering parallel to the surface, while, in case iii, weaker dispersion and packing interactions are unable to bring aliphatic tails together into mesoscopic islands, against overwhelming entropy and Coulomb forces. The onset of in-plane mesophases could greatly affect the properties of long-chain RTILs used as lubricants. PMID:19886615

  11. Proactive aquatic ecotoxicological assessment of room-temperature ionic liquids

    USGS Publications Warehouse

    Kulacki, K.J.; Chaloner, D.T.; Larson, J.H.; Costello, D.M.; Evans-White, M. A.; Docherty, K.M.; Bernot, R.J.; Brueseke, M.A.; Kulpa, C.F.; Lamberti, G.A.

    2011-01-01

    Aquatic environments are being contaminated with a myriad of anthropogenic chemicals, a problem likely to continue due to both unintentional and intentional releases. To protect valuable natural resources, novel chemicals should be shown to be environmentally safe prior to use and potential release into the environment. Such proactive assessment is currently being applied to room-temperature ionic liquids (ILs). Because most ILs are water-soluble, their effects are likely to manifest in aquatic ecosystems. Information on the impacts of ILs on numerous aquatic organisms, focused primarily on acute LC50 and EC50 endpoints, is now available, and trends in toxicity are emerging. Cation structure tends to influence IL toxicity more so than anion structure, and within a cation class, the length of alkyl chain substituents is positively correlated with toxicity. While the effects of ILs on several aquatic organisms have been studied, the challenge for aquatic toxicology is now to predict the effects of ILs in complex natural environments that often include diverse mixtures of organisms, abiotic conditions, and additional stressors. To make robust predictions about ILs will require coupling of ecologically realistic laboratory and field experiments with standard toxicity bioassays and models. Such assessments would likely discourage the development of especially toxic ILs while shifting focus to those that are more environmentally benign. Understanding the broader ecological effects of emerging chemicals, incorporating that information into predictive models, and conveying the conclusions to those who develop, regulate, and use those chemicals, should help avoid future environmental degradation. ?? 2011 Bentham Science Publishers Ltd.

  12. Microstructure of room temperature ionic liquids at stepped graphite electrodes

    DOE PAGESBeta

    Feng, Guang; Li, Song; Zhao, Wei; Cummings, Peter T.

    2015-07-14

    Molecular dynamics simulations of room temperature ionic liquid (RTIL) [emim][TFSI] at stepped graphite electrodes were performed to investigate the influence of the thickness of the electrode surface step on the microstructure of interfacial RTILs. A strong correlation was observed between the interfacial RTIL structure and the step thickness in electrode surface as well as the ion size. Specifically, when the step thickness is commensurate with ion size, the interfacial layering of cation/anion is more evident; whereas, the layering tends to be less defined when the step thickness is close to the half of ion size. Furthermore, two-dimensional microstructure of ionmore » layers exhibits different patterns and alignments of counter-ion/co-ion lattice at neutral and charged electrodes. As the cation/anion layering could impose considerable effects on ion diffusion, the detailed information of interfacial RTILs at stepped graphite presented here would help to understand the molecular mechanism of RTIL-electrode interfaces in supercapacitors.« less

  13. Applications of room temperature ionic liquids in interfacial polymerization

    NASA Astrophysics Data System (ADS)

    Zhu, Lining

    2006-12-01

    Room temperature ionic liquids (ILs), with their unique physical and chemical properties, have been of great interest in various areas of chemical science and engineering during the last decade. In this dissertation, polyurea and polyamide films with surface nanostructures were synthesized by interfacial polymerization (IP) with ILs without stirring. Both polymers were prepared at the interface between n-hexane and a series of 1-alkyl-3-methylimidazolium ILs. Nanoporous or nanofibrous polymer morphologies with various sizes ranging from 50 to 500 nm and geometries, depending on the ILs used, were observed by scanning electron microscopy (SEM). A correlation length of ˜20nm and a suppression of three-dimensional (3-D) crystalline structure of the polyurea were found by small angle X-ray scattering (SAXS) and X-ray diffraction (XRD), respectively. FTIR spectra showed no significant changes in the chemical composition of the polymer by the employment of ILs. The peculiar nanostructure of the polymer could be ascribed to the intermolecular interactions between the ILs and the polymer, which affected the development of the polymer morphology. The polyamides prepared with ILs showed larger intrinsic viscosities, and consequently higher molecular weights, compared to the one prepared without ILs; this could be due to the prevention of the side reaction between sebacoyl chloride and water. The enhancement of the molecular weight renders a better thermal stability to the polyamide film, as revealed by thermogravimetric analysis (TGA) which showed a higher decomposition temperature. Coating of fine particulates with polyurea by IP has been developed. With increasing stirring speed in the coating process, a decreased mean particle size and a narrower particle size distribution, as well as a lower coating weight percentage were found by particle size analysis and TGA, respectively. A Porous coating layer was formed in the IP coating in the presence of ILs. The reaction

  14. Sound velocity dispersion in room temperature ionic liquids studied using the transient grating method.

    PubMed

    Fukuda, M; Terazima, M; Kimura, Y

    2008-03-21

    Sound velocity is determined by the transient grating method in a range from 10(6) to 10(10) Hz in three room temperature ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, and N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide. In all room temperature ionic liquids studied, the sound velocity increased with increasing frequency. The cause of this change is posited to be structural relaxation in the room temperature ionic liquids. Frequency dependence of the sound velocity is not reproduced by a simple Debye relaxation model. The sound velocity dispersion relation in 1-butyl-3-methylimidazolium hexafluorophosphate matches a Cole-Davidson function with parameters determined by a dielectric relaxation [C. Daguenet et al., J. Phys. Chem. B 110, 12682 (2006)], indicating that structural and reorientational relaxations are strongly coupled. Conversely, the sound velocity dispersions of the other two ionic liquids measured do not match those measured for dielectric relaxation, implying that structural relaxation is much faster than the reorientational relaxation. This difference is discussed in relation to the motilities of anions and cations. PMID:18361592

  15. Anion pairs in room temperature ionic liquids predicted by molecular dynamics simulation, verified by spectroscopic characterization

    SciTech Connect

    Schwenzer, Birgit; Kerisit, Sebastien N.; Vijayakumar, M.

    2014-01-01

    Molecular-level spectroscopic analyses of an aprotic and a protic room-temperature ionic liquid, BMIM OTf and BMIM HSO4, respectively, have been carried out with the aim of verifying molecular dynamics simulations that predict anion pair formation in these fluid structures. Fourier-transform infrared spectroscopy, Raman spectroscopy and nuclear magnetic resonance spectroscopy of various nuclei support the theoretically-determined average molecular arrangements.

  16. Decoupling charge transport from the structural dynamics in room temperature ionic liquids

    SciTech Connect

    Griffin, Phillip; Agapov, Alexander L; Kisliuk, Alexander; Sun, Xiao-Guang; Dai, Sheng; Novikov, Vladimir; Sokolov, Alexei P

    2011-01-01

    Light scattering and dielectric spectroscopy measurements were performed on the room temperature ionic liquid (RTIL) [C4mim][NTf2] in a broad temperature and frequency range. Ionic conductivity was used to estimate self-diffusion of ions, while light scattering was used to study structural relaxation. We demonstrate that the ionic diffusion decouples from the structural relaxation process as the temperature of the sample decreases toward Tg. The strength of the decoupling appears to be significantly lower than that expected for a supercooled liquid of similar fragility. The structural relaxation process in the RTIL follows well the high-temperature mode coupling theory (MCT) scenario. Using the MCT analysis we estimated the dynamic crossover temperature in [C4mim][NTf2] to be Tc 225 5 K. However, our analysis reveals no sign of the dynamic crossover in the ionic diffusion process.

  17. DEVELOPMENT OF ROOM TEMPERATURE IONIC LIQUIDS FOR APPLICATIONS IN ACTINIDE CHEMISTRY

    SciTech Connect

    W. OLDHAM; D. COSTA; W. SMITH

    2001-05-01

    One area of on-going research in our group at Los Alamos National Laboratory is directed toward characterization of the basic coordination chemistry and electrochemical behavior of f-element ions dissolved in room temperature ionic liquids (RTILs). The ultimate goal of this work is to introduce advanced, environmentally sustainable, nuclear processing and purification strategies into both the DOE complex and the civilian nuclear industry. Efforts to develop ambient temperature electrorefining and/or electrowinning technologies are focused on the design of ionic liquids characterized by extended cathodic stability. In this chapter a summary of the synthesis, physical properties and electrochemical behavior of the ionic liquids used in this work is presented. The feasibility of efficient electrochemical production of high electropositive metals is demonstrated through reversible plating and stripping of sodium and potassium metals.

  18. Supported Room Temperature Ionic Liquid Membranes for CO{sub 2}/CH{sub 4} Separation

    SciTech Connect

    Iarikov, D. D.; Hacarlioglu, P.; Oyama, S. T.

    2011-01-01

    Room temperature ionic liquids (RTILs) are organic salts which are liquid at or around room temperature. These compounds exhibit many outstanding physical properties such as great thermal stability and no measurable vapor pressure. In this work supported ionic liquid membranes (SILMs) were prepared by impregnating pores of α-alumina inorganic supports with various ionic liquids. In addition to membranes prepared with pure RTILs we were able to synthesize membranes with RTIL mixtures using 1-aminopyridinium iodide dissolved in 1-butyl-4-methylpyridinium tetrafluoroborate or methyltrioctylammonium bis(trifluoromethylsulfonyl)imide. This combination of an RTIL with an organic salt containing an amine group dramatically improved the membrane separation properties. The SILMs displayed CO{sub 2} permeance on the order of 5 × 10{sup −10} to 5 × 10{sup −9} mol m{sup −2} s{sup −1} Pa{sup −1} combined with CO{sub 2}/CH{sub 4} selectivity of 5–30. Although these values are comparable with the current systems for CO{sub 2} purification, CO{sub 2} permeance is still rather low for these compounds.

  19. Benzyl-Functionalized Room Temperature Ionic Liquids for CO2/N2 Separation

    SciTech Connect

    Mahurin, Shannon Mark; Dai, Thomas N; Yeary, Joshua S; Luo, Huimin; Dai, Sheng

    2011-01-01

    In this work, three classes of room temperature ionic liquids (RTILs), including imidazolium, pyridinium, and pyrrolidinium ionic liquids with a benzyl group appended to the cation, were synthesized and tested for their performance in separating CO{sub 2} and N{sub 2}. All RTILs contained the bis(trifluoromethylsulfonyl)imide anion, permitting us to distinguish the impact of the benzyl moiety attached to the cation on gas separation performance. In general, the attachment of the benzyl group increased the viscosity of the ionic liquid compared with the unfunctionalized analogs and decreased the CO{sub 2} permeability. However, all of the benzyl-modified ionic liquids exhibited enhanced CO{sub 2}/N{sub 2} selectivities compared with alkyl-based ionic liquids, with values ranging from 22.0 to 33.1. In addition, CO{sub 2} solubilities in the form of Henry's constants were also measured and compared with unfunctionalized analogs. Results of the membrane performance tests and CO{sub 2} solubility measurements demonstrate that the benzyl-functionalized RTILs have significant potential for use in the separation of carbon dioxide from combustion products.

  20. Morphology of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Triolo, Alessandro; Russina, Olga; Fazio, Barbara; Triolo, Roberto; Di Cola, Emanuela

    2008-05-01

    The structural organization in selected room temperature ionic liquids, namely (a) butyl-, (b) hexyl- and (c) octyl-3-methylimidazolium hexafluorophosphate, is investigated by means of X-ray diffraction. We find novel experimental evidences of the existence of a high degree of intermediate range order that is associated to nanoscale segregation of the alkyl chains into the charged matrix. The size of these structural heterogeneities depends linearly from the alkyl chain length. A similar behaviour had been observed in other systems, such as normal alcohols. The slope of such dependence provides hints on the nature of the structural organization of these segregated domains.

  1. Room Temperature Ionic Liquids as Green Solvent Alternatives in the Metathesis of Oleochemical Feedstocks.

    PubMed

    Thomas, Priya A; Marvey, Bassy B

    2016-01-01

    One of the most important areas of green chemistry is the application of environmentally friendly solvents in catalysis and synthesis. Conventional organic solvents pose a threat to the environment due to the volatility, highly flammability, toxicity and carcinogenic properties they exhibit. The recently emerged room temperature ionic liquids (RTILs) are promising green solvent alternatives to the volatile organic solvents due to their ease of reuse, non-volatility, thermal stability and ability to dissolve a variety of organic and organometallic compounds. This review explores the use of RTILs as green solvent media in olefin metathesis for applications in the oleochemical industry. PMID:26861282

  2. Facile room temperature deposition of gold nanoparticle-ionic liquid hybrid film on silica substrate.

    PubMed

    Krishnamurthy, S; Reddy, D Harikishore Kumar; Sankar, G; Yun, Yeoung-Sang

    2017-01-01

    This work presents facile synthesis of gold nanoparticle (Au NP)-ionic liquid hybrid film of <10nm by a simple two-step process at room temperature by deposition of Au NPs suspended in 1-hexyl-1methyl-pyrolidinium bromide, on Si (111) substrates. FTIR results demonstrated that ionic liquid properties remain unaltered during and after Au NP synthesis, and even coating on Si (111) substrate. XRD, XPS, and XAS spectral data confirm the presence of Au(0) while EXAFS data indicated the presence of small particles or incomplete surface species. Cross-sectional analysis using FE-SEM and edge length measurement using AFM showed that the film thickness is ca 10nm. PMID:27415970

  3. SEM Observation of Hydrous Superabsorbent Polymer Pretreated with Room-Temperature Ionic Liquids

    PubMed Central

    Tsuda, Tetsuya; Mochizuki, Eiko; Kishida, Shoko; Iwasaki, Kazuki; Tsunashima, Katsuhiko; Kuwabata, Susumu

    2014-01-01

    Room-temperature ionic liquid (RTIL), which is a liquid salt at or below room temperature, shows peculiar physicochemical properties such as negligible vapor pressure and relatively-high ionic conductivity. In this investigation, we used six types of RTILs as a liquid material in the pretreatment process for scanning electron microscope (SEM) observation of hydrous superabsorbent polymer (SAP) particles. Very clear SEM images of the hydrous SAP particles were obtained if the neat RTILs were used for the pretreatment process. Of them, tri-n-butylmethylphosphonium dimethylphosphate ([P4, 4, 4, 1][DMP]) provided the best result. On the other hand, the surface morphology of the hydrous SAP particles pretreated with 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) was damaged. The results of SEM observation and thermogravimetry analysis of the hydrous SAP pretreated with the RTILs strongly suggested that most water in the SAP particles are replaced with RTIL during the pretreatment process. PMID:24621609

  4. Electrochemical studies of hydrogen chloride gas in several room temperature ionic liquids: mechanism and sensing.

    PubMed

    Murugappan, Krishnan; Silvester, Debbie S

    2016-01-28

    The electrochemical behaviour of highly toxic hydrogen chloride (HCl) gas has been investigated in six room temperature ionic liquids (RTILs) containing imidazolium/pyrrolidinium cations and range of anions on a Pt microelectrode using cyclic voltammetry (CV). HCl gas exists in a dissociated form of H(+) and [HCl2](-) in RTILs. A peak corresponding to the oxidation of [HCl2](-) was observed, resulting in the formation of Cl2 and H(+). These species were reversibly reduced to H2 and Cl(-), respectively, on the cathodic CV scan. The H(+) reduction peak is also present initially when scanned only in the cathodic direction. In the RTILs with a tetrafluoroborate or hexafluorophosphate anion, CVs indicated a reaction of the RTIL with the analyte/electrogenerated products, suggesting that these RTILs might not be suitable solvents for the detection of HCl gas. This was supported by NMR spectroscopy experiments, which showed that the hexafluorophosphate ionic liquid underwent structural changes after HCl gas electrochemical experiments. The analytical utility was then studied in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) by utilising both peaks (oxidation of [HCl2](-) and reduction of protons) and linear calibration graphs for current vs. concentration for the two processes were obtained. The reactive behaviour of some ionic liquids clearly shows that the choice of the ionic liquid is very important if employing RTILs as solvents for HCl gas detection. PMID:26697927

  5. Structure of the room-temperature ionic liquid 1-hexyl-3-methylimidazolium hydrogen sulfate: conformational isomerism.

    PubMed

    Kiefer, Johannes; Pye, Cory C

    2010-06-24

    The acidic room-temperature ionic liquid 1-hexyl-3-methylimidazolium hydrogen sulfate has recently been identified to have beneficial properties for practical applications in catalysis and electrochemistry. In the present work, the conformational isomerism of this ionic liquid is studied by means of density functional theory calculations and experiments in terms of infrared absorption and Raman scattering spectroscopy. For the hydrogen sulfate anion, the trans conformer is found to be the favored isomer in the ionic liquid. For the 1-hexyl-3-methylimidazolium cation, three different low-energy conformations were obtained, differing only in the orientation of the hexyl chain. The comparison of vibrational frequencies with IR and Raman data showed good agreement for all three conformations, indicating their presence in the ionic liquid. Beyond revealing the conformational information, the experimental spectra indicate strong interionic interactions. Vibrations of sulfuric acid could be observed, indicating possible proton transfer from the cation to the anion. This is further supported by the appearance of modes around 2000 cm(-1) in the IR spectrum, which could tentatively be assigned to C2-H stretching vibrations red-shifted as a result of strong interionic hydrogen bonds as a prerequisite of proton transfer. PMID:20509684

  6. Mechanisms of metal ion transfer into room-temperature ionic liquids : the role of anion exchange.

    SciTech Connect

    Jensen, M. P.; Neuefeind, J.; Beitz, J. V.; Skanthakumar, S.; Soderholm, L.; Chemistry

    2003-12-17

    The structure and stoichiometry of the lanthanide(III) (Ln) complexes with the ligand 2-thenoyltrifluoroacetone (Htta) formed in a biphasic aqueous room-temperature ionic liquid system have been studied by complementary physicochemical methods. Equilibrium thermodynamics, optical absorption and luminescence spectroscopies, high-energy X-ray scattering, EXAFS, and molecular dynamics simulations all support the formation of anionic Nd(tta){sub 4}{sup -} or Eu(tta){sub 4}{sup -} complexes with no water coordinated to the metal center in 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C{sub 4}mim{sup +}Tf{sub 2}N{sup -}), rather than the hydrated, neutral complexes, M(tta){sub 3}(H{sub 2}O){sub n} (n = 2 or 3), that form in nonpolar molecular solvents, such as xylene or chloroform. The presence of anionic lanthanide complexes in C{sub 4}mim{sup +}Tf{sub 2}N{sup -} is made possible by the exchange of the ionic liquid anions into the aqueous phase for the lanthanide complex. The resulting complexes in the ionic liquid phase should be thought of as weak C{sub 4}mim{sup +}Ln(tta){sub 4}{sup -} ion pairs which exert little influence on the structure of the ionic liquid phase.

  7. Translation-rotation decoupling and nonexponentiality in room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Griffin, Philip; Agapov, Alexander; Sokolov, Alexei

    2013-03-01

    It is generally accepted that room temperature ionic liquids (RTILs) have many characteristics in common with prototypical molecular glass formers. In order to understand the glassy dynamics of RTILs, we have measured the temperature dependence of structural relaxation time and self diffusion in three imidazolium based RTILs. We demonstrate that self diffusion decouples from structural relaxation in these systems as the temperature is decreased toward Tg, but the degree of decoupling is shown to be exceptionally small. In addition to the weak decoupling, we demonstrate that the temperature dependence of structural relaxation time in all three liquids can be well described by a single Vogel-Fulcher-Tammann (VFT) function over 13 decades in time. Furthermore, the stretching of the structural relaxation is shown to be temperature independent over the same range of timescales, i.e. time-temperature superposition is valid for these ionic liquids in the entire temperature range. These properties are at odds with the usual behavior of most ``fragile'' glass forming liquids. We suggest that these differences may result from strong and directional intermolecular interactions characteristic to RTILs.

  8. Translation-rotation decoupling and nonexponentiality in room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Griffin, Philip J.; Agapov, Alexander L.; Sokolov, Alexei P.

    2012-08-01

    Using a combination of light scattering techniques and broadband dielectric spectroscopy, we have measured the temperature dependence of structural relaxation time and self diffusion in three imidazolium-based room temperature ionic liquids: [bmim][NTf2], [bmim][PF6], and [bmim][TFA]. A detailed analysis of the results demonstrates that self diffusion decouples from structural relaxation in these systems as the temperature is decreased toward Tg. The degree to which the dynamics are decoupled, however, is shown to be surprisingly weak when compared to other supercooled liquids of similar fragility. In addition to the weak decoupling, we demonstrate that the temperature dependence of the structural relaxation time in all three liquids can be well described by a single Vogel-Fulcher-Tamann function over 13 decades in time from 10-11 s up to 102 s. Furthermore, the stretching of the structural relaxation is shown to be temperature independent over the same range of time scales, i.e., time temperature superposition is valid for these ionic liquids from far above the melting point down to the glass transition temperature. We suggest that these phenomena are interconnected and all result from the same underlying mechanism—strong and directional intermolecular interactions.

  9. Layered structure of room-temperature ionic liquids in microemulsions by multinuclear NMR spectroscopic studies.

    PubMed

    Falcone, R Dario; Baruah, Bharat; Gaidamauskas, Ernestas; Rithner, Christopher D; Correa, N Mariano; Silber, Juana J; Crans, Debbie C; Levinger, Nancy E

    2011-06-01

    Microemulsions form in mixtures of polar, nonpolar, and amphiphilic molecules. Typical microemulsions employ water as the polar phase. However, microemulsions can form with a polar phase other than water, which hold promise to diversify the range of properties, and hence utility, of microemulsions. Here microemulsions formed by using a room-temperature ionic liquid (RTIL) as the polar phase were created and characterized by using multinuclear NMR spectroscopy. (1)H, (11)B, and (19)F NMR spectroscopy was applied to explore differences between microemulsions formed by using 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) as the polar phase with a cationic surfactant, benzylhexadecyldimethylammonium chloride (BHDC), and a nonionic surfactant, Triton X-100 (TX-100). NMR spectroscopy showed distinct differences in the behavior of the RTIL as the charge of the surfactant head group varies in the different microemulsion environments. Minor changes in the chemical shifts were observed for [bmim](+) and [BF(4)](-) in the presence of TX-100 suggesting that the surfactant and the ionic liquid are separated in the microemulsion. The large changes in spectroscopic parameters observed are consistent with microstructure formation with layering of [bmim](+) and [BF(4)](-) and migration of Cl(-) within the BHDC microemulsions. Comparisons with NMR results for related ionic compounds in organic and aqueous environments as well as literature studies assisted the development of a simple organizational model for these microstructures. PMID:21547960

  10. Direct electrochemistry of cytochrome c entrapped in agarose hydrogel in room temperature ionic liquids.

    PubMed

    Wang, Sui; Guo, Zhiyong; Zhang, Huina

    2011-08-01

    Direct electrochemistry of cytochrome c (cyt-c) entrapped in agarose hydrogel on gold electrode (Au), edge plane pyrolytic graphite electrode (EPPGE) and glassy carbon electrode (GC) in two room temperature ionic liquids was investigated. The effects of the addition of N,N-dimethylformamide (DMF) in the agarose-cyt-c film, water concentration in ionic liquids and exterior metal ions on the electrochemical behavior of cyt-c were monitored, and electrocatalytic properties of cyt-c were also done. Results showed that a good quasi-reversible redox behavior of cyt-c could be found after adding DMF in agarose-cyt-c film, and peak shape would not change after continuously scanning for 50 cycles. In addition, a certain amount of water in hydrophilic ionic liquids is necessary to maintain electrochemical activities of cyt-c, electrochemical performance of cyt-c is the best when the water content is 5.2% and 5.8% for 1-butyl-3-methylimidazolium bromide ([Bmim][Br]) and 1-butyl-3-methylimidazolium tetrafluoroborate([Bmim][BF(4)]) respectively. However, electrochemical activities of cyt-c are inhibited by exterior metal ions. Interestingly, cyt-c entrapped in agarose hydrogel on EPPGE and GC could catalyze the electroreduction of trichloroacetic acid (TCA) and tert-butyl hydroperoxide (t-BuOOH) in [Bmim][BF(4)], but could not in [Bmim][Br]. Reasons for above-mentioned differences of electrochemical properties of cyt-c in different ionic liquids were preliminarily discussed. PMID:21659008

  11. Solute-solvent hydrogen-bonding in room temperature ionic liquids studied by Raman spectroscopy.

    PubMed

    Kobayashi, Akira; Osawa, Koji; Terazima, Masahide; Kimura, Yoshifumi

    2012-10-21

    The vibrational frequencies of the C=O + C=C band of diphenylcyclopropenone and the NH(2) stretching band of p-aminobenzonitrile were determined in various room temperature ionic liquids (RTILs). The vibrational frequency shifts of the C=O + C=C stretching mode were compared with Kamlet α values, and frequency shifts of the NH(2) stretching mode were compared with Kamlet β values. A nearly linear relationship was obtained for both parameters, although the solvatochromic parameters were more sensitive to changes of the cation species. Vibrational frequency calculations of a 1 : 1 cluster of p-aminobenzonitrile with the RTIL anions using DFT theory reproduced the observed frequency shifts of the NH(2) stretching mode fairly well. The frequency shifts of the CN stretching mode were well reproduced by the linear combination of dipolarity parameters, the hydrogen-bond donating and accepting parameters determined by the Raman shift of the solute molecule. PMID:22968223

  12. Observation of electrodeposited lithium by optical microscope in room temperature ionic liquid-based electrolyte

    NASA Astrophysics Data System (ADS)

    Sano, H.; Sakaebe, H.; Matsumoto, H.

    Room temperature ionic liquids (RTILs) were applied to a lithium (Li) metal battery system, and the behavior of Li electrodeposition on nickel electrodes in RTILs was investigated using in situ optical microscopy with/without an organic additive, vinylene carbonate (VC), in the RTILs. Two RTILs, PP13[TFSA] (N-methyl- N-propylpiperidinium bis(trifluoromethanesulfonyl)amide) and EMI[FSA] (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide), were chosen as the base electrolytes. Dendritic particles were obtained in the case of EMI[FSA] with and without VC, and PP13[TFSA] without VC, while non-dendritic fine particles were obtained in the case of PP13[TFSA] with VC.

  13. Cellulose gels produced in room temperature ionic liquids by ionizing radiation

    NASA Astrophysics Data System (ADS)

    Kimura, Atsushi; Nagasawa, Naotsugu; Taguchi, Mitsumasa

    2014-10-01

    Cellulose-based gels were produced in room temperature ionic liquids (RTILs) by ionizing radiation. Cellulose was dissolved at the initial concentration of 20 wt% in 1-ethyl-3-methylimidazolium (EMI)-acetate or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (DEMA)-formate with a water content of 18 wt%, and irradiated with γ-rays under aerated condition to produce new cellulose gels. The gel fractions of the cellulose gels obtained in EMI-acetate and DEMA-formate at a dose of 10 kGy were 13% and 19%, respectively. The formation of gel fractions was found to depend on the initial concentration of cellulose, water content, and irradiation temperature. The obtained gel readily absorbed water, methanol, ethanol, dichloromethane, N,N-dimethylacetamide, and RTILs.

  14. Free Radical Polymerization of Styrene and Methyl Methacrylate in Various Room Temperature Ionic Liquids

    SciTech Connect

    Zhang, Hongwei; Hong, Kunlun; Mays, Jimmy

    2005-01-01

    Conventional free radical polymerization of styrene and methyl methacrylate was carried out in various room temperature ionic liquids (RTILs). The RTILs used in this research encompass a wide range of cations and anions. Typical cations include imidazolium, phosphonium, pyridinium, and pyrrolidinium; typical anions include amide, borate, chloride, imide, phosphate, and phosphinate. Reactions are faster and polymers obtained usually have higher molecular weights when compared to polymerizations carried out in volatile organic solvents under the same conditions. This shows that rapid rates of polymerization and high molecular weights are general features of conventional radical polymerizations in RTILs. Attempts to correlate the polarities and viscosities of the RTILs with the polymerization behavior fail to yield discernible trends.

  15. Scanning Electron Microscope Observation of Carbon Nanotubes with Room Temperature Ionic Liquids: Effect of Their Hydrophilicities.

    PubMed

    Hyono, Atsushi; Abe, Shigeaki; Kawai, Koji; Yonezawa, Tetsu

    2015-11-01

    In this study, we succeeded in acquiring scanning electron microscope (SEM) images of carbon nanotube (CNT) derivatives with different surface properties based on an electro-conductive pretreatment using a room temperature ionic liquid (IL). The quality of the obtained SEM images depended on their surface properties and the hydrophilicities of IL used. When the hydrophilicities of both the sample surface and the IL were close, the obtained SEM images had a high resolution. In contrast, SEM imges of samples pretreated with an IL, which had different hydrophilicities from the sample, was observed with low resolution and low quality. This result suggests that the relationship between both hydrophilicities is the dominant factor for this visualization method. PMID:26726681

  16. Study on the reaction of chlorophenols in room temperature ionic liquids with ionizing radiation

    NASA Astrophysics Data System (ADS)

    Kimura, Atsushi; Taguchi, Mitsumasa; Kondoh, Takafumi; Yang, Jinfeng; Yoshida, Yoichi; Hirota, Koichi

    2008-10-01

    The effects of cations and anions of room temperature ionic liquids (RTILs) on the decomposition of chlorophenols and formation of phenol were investigated by gamma and pulse radiolyses. Absorption bands were observed for aliphatic RTILs just after pulsed electron irradiation, and were assigned as solvated electrons. The decomposition yield of chlorophenol (CP), G(-CP), and the formation yield of phenol, G(Phenol), in RTILs, in which solvated electrons were observed, were higher than those in RTILs, in which the solvated electrons were not detected. G(-CP) and G(Phenol) increased with the viscosity of the RTILs which have diethylmethyl(2-methoxyethyl)ammonium (DEMMA) as cation. G(Phenol) in DEMMA-bis(trifluoromethylsulfonyl)imide (TFSI) having high viscosity was higher than that in trimethylpropylammonium (TMPA)-TFSI having low viscosity. The ratios of G(Phenol)/ G(-CP) were not affected by the substituted position of chlorine on CP in RTILs.

  17. Non-Faradaic Energy Storage by Room Temperature Ionic Liquids in Nanoporous Electrodes.

    PubMed

    Vatamanu, Jenel; Vatamanu, Mihaela; Bedrov, Dmitry

    2015-06-23

    The enhancement of non-Faradaic charge and energy density stored by ionic electrolytes in nanostructured electrodes is an intriguing issue of great practical importance for energy storage in electric double layer capacitors. On the basis of extensive molecular dynamics simulations of various carbon-based nanoporous electrodes and room temperature ionic liquid (RTIL) electrolytes, we identify atomistic mechanisms and correlations between electrode/electrolyte structures that lead to capacitance enhancement. In the symmetric electrode setup with nanopores having atomically smooth walls, most RTILs showed up to 50% capacitance increase compared to infinitely wide pore. Extensive simulations using asymmetric electrodes and pores with atomically rough surfaces demonstrated that tuning of electrode nanostructure could lead to further substantial capacitance enhancement. Therefore, the capacitance in nanoporous electrodes can be increased due to a combination of two effects: (i) the screening of ionic interactions by nanopore walls upon electrolyte nanoconfinement, and (ii) the optimization of nanopore structure (volume, surface roughness) to take into account the asymmetry between cation and anion chemical structures. PMID:26038979

  18. Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

    SciTech Connect

    Griffin, Philip J.; Holt, Adam P.; Tsunashima, Katsuhiko; Sangoro, Joshua R.; Kremer, Friedrich; Sokolov, Alexei P.

    2015-02-28

    Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.

  19. Heats of vaporization of room temperature ionic liquids by tunable vacuum ultraviolet photoionization

    SciTech Connect

    Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; To, Albert; Koh, Christine; Strasser, Daniel; Kostko, Oleg; Leone, Stephen R.

    2009-11-25

    The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be Delta Hvap(298.15 K) = 195+-19 kJ mol-1. The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (Delta Hvap(298.15 K) = 174+-12 kJ mol-1) and N-butyl-N-methylpyrrolidinium dicyanamide (Delta Hvap(298.15 K) = 171+-12 kJ mol-1) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion ion pairs.

  20. Room-temperature ionic liquids enhanced green synthesis of β-glycosyl 1-ester.

    PubMed

    Cui, Yanli; Xu, Minghan; Yao, Weirong; Mao, Jianwei

    2015-04-30

    We herein report an efficient synthesis of β-glycosyl 1-ester in room-temperature ionic liquids (RTILs) promoted via silver salt and quaternary ammonium salt (PTC) with good or excellent yields. All products were isolated exclusively as the β-anomers. Four different RTILs, eight metal salts and four quaternary ammonium salts were screened in the glycosylation reaction. The synergistic effect of C6mim·OTf, Ag2O and tetrabutylammonium iodine gave the best results. Their promotion to the system was integral. Thorough study provided insight into the catalytic activity of ionic liquid structure, metal salts and quaternary ammonium salt to these reactions. It is worth mentioning that the yield of aliphatic compound 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl butyrate (3l) was highly improved when using C6mim·OTf as solvent compared with the normal volatile solvents under the same catalysts. This green approach has been proved to be practical and compatible with a wide range from aliphatic to aromatic substrates. PMID:25704198

  1. Room temperature ionic liquids interacting with bio-molecules: an overview of experimental and computational studies

    NASA Astrophysics Data System (ADS)

    Benedetto, Antonio; Ballone, Pietro

    2016-03-01

    We briefly review experimental and computational studies of room temperature ionic liquids (RTILs) interacting with important classes of biomolecules, including phospholipids, peptides and proteins, nucleic acids and carbohydrates. Most of these studies have been driven by the interest for RTILs applications as solvents. Thus, available experimental data cover primarily thermodynamic properties such as the reciprocal solubility of RTILs and bio-molecules, as well as phase boundaries. Less extensive data are also available on transport properties such as diffusion and viscosity of homogeneous binary (RTILs/biomolecules) and ternary (RTIL/biomolecules/water) solutions. Most of the structural information at the atomistic level, of interest especially for biochemical, pharmaceutical and nanotechnology applications, has been made available by molecular dynamics simulations. Major exceptions to this statement are represented by the results from NMR and circular dichroism spectroscopy, by selected neutron and X-ray scattering data, and by recent neutron reflectometry measurements on lipid bilayers on surfaces, hydrated by water-RTIL solutions. A final section of our paper summarizes new developments in the field of RTILs based on amino acids, that combine in themselves the two main aspects of our discussion, i.e. ionic liquids and bio-molecules.

  2. Ionic liquid pretreatment of poplar wood at room temperature: swelling and incorporation of nanoparticles

    SciTech Connect

    Lucas, Marcel; Macdonald, Brian A; Wagner, Gregory L; Joyce, Steven A; Rector, Kirk D

    2010-01-01

    Lignocellulosic biomass represents a potentially sustainable source of liquid fuels and commodity chemicals. It could satisfy the energy needs for transportation and electricity generation, while contributing substantially to carbon sequestration and limiting the accumulation of greenhouse gases in the atmosphere. Potential feedstocks are abundant and include crops, agricultural wastes, forest products, grasses, and algae. Among those feedstocks, wood is mainly constituted of three components: cellulose, hemicellulose, and lignin. The conversion process of lignocellulosic biomass typically consists of three steps: (1) pretreatment; (2) hydrolysis of cellulose and hemicellulose into fermentable sugars; and (3) fermentation of the sugars into liquid fuels (ethanol) and other commodity chemicals. The pretreatment step is necessary due to the complex structure of the plant cell wall and the chemical resistance of lignin. Most current pretreatments are energy-intensive and/or polluting. So it is imperative to develop new pretreatments that are economically viable and environmentally friendly. Recently, ionic liquids have attracted considerable interest, due to their ability to dissolve biopolymers, such as cellulose, lignin, native switchgrass, and others. Ionic liquids are also considered green solvents, since they have been successfully recycled at high yields for further use with limited efficiency loss. Also, a few microbial cellulases remain active at high ionic liquid concentration. However, all studies on the dissolution of wood in ionic liquids have been conducted so far at high temperatures, typically above 90 C. Development of alternative pretreatments at room temperature is desirable to eliminate the additional energy cost. In this study, thin sections of poplar wood were swollen at room temperature by a 3 h ionic liquid (1-ethyl-3-methylimidazolium acetate or EMIMAc) pretreatment. The pretreated sample was then exposed to an aqueous suspension of

  3. Magnetomotive room temperature dicationic ionic liquid: a new concept toward centrifuge-less dispersive liquid-liquid microextraction.

    PubMed

    Beiraghi, Asadollah; Shokri, Masood; Seidi, Shahram; Godajdar, Bijan Mombani

    2015-01-01

    A new centrifuge-less dispersive liquid-liquid microextraction technique based on application of magnetomotive room temperature dicationic ionic liquid followed by electrothermal atomic absorption spectrometry (ETAAS) was developed for preconcentration and determination of trace amount of gold and silver in water and ore samples, for the first time. Magnetic ionic liquids not only have the excellent properties of ionic liquids but also exhibit strong response to an external magnetic field. These properties provide more advantages and potential application prospects for magnetic ionic liquids than conventional ones in the fields of extraction processes. In this work, thio-Michler's ketone (TMK) was used as chelating agent to form Ag/Au-TMK complexes. Several important factors affecting extraction efficiency including extraction time, rate of vortex agitator, pH of sample solution, concentration of the chelating agent, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) were 3.2 and 7.3ngL(-1) with the preconcentration factors of 245 and 240 for Au and Ag, respectively. The precision values (RSD%, n=7) were 5.3% and 5.8% at the concentration level of 0.05μgL(-1) for Au and Ag, respectively. The relative recoveries for the spiked samples were in the acceptable range of 96-104.5%. The results demonstrated that except Hg(2+), no remarkable interferences are created by other various ions in the determination of Au and Ag, so that the tolerance limits (WIon/WAu or Ag) of major cations and anions were in the range of 250-1000. The validated method was successfully applied for the analysis of Au and Ag in some water and ore samples. PMID:25528072

  4. Supported Phospholipid Bilayer Defects Created by a Cation or Anion of a Room-Temperature Ionic Liquid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this work, the independent effects on a supported phospholipid bilayer (SPB) caused by a cation and anion of a room-temperature ionic liquid (RT-IL) were studied via atomic force microscopy (AFM). The supported phospholipid bilayer was composed only of 1,2-dielaidoylphosphatidylcholine (DEPC) an...

  5. Guide to CO{sub 2} separations in imidazolium-based room-temperature ionic liquids

    SciTech Connect

    Bara, J.E.; Carlisle, T.K.; Gabriel, C.J.; Camper, D.; Finotello, A.; Gin, D.L.; Noble, R.D.

    2009-03-18

    Room-temperature ionic liquids (RTILs) are nonvolatile, tunable solvents. The solubilities of gases, particularly CO{sub 2}, N{sub 2}, and CH{sub 4}, have been studied in a number of RTILs. Process temperature and the chemical structures of the cation and anion have significant impacts on gas solubility and gas pair selectivity. Models based on regular solution theory and group contributions are useful to predict and explain CO{sub 2} solubility and selectivity in imidazolium-based RTILs. In addition to their role as a physical solvent, RTILs might also be used in supported ionic liquid membranes (SILMs) as a highly permeable and selective transport medium. Performance data for SILMs indicates that they exhibit large permeabilities as well as CO{sub 2}/N{sub 2} selectivities that outperform many polymer membranes. Furthermore, the greatest potential of RTILs for CO{sub 2} separations might lie in their ability to chemically capture CO{sub 2} when used in combination with amines. Amines can be tethered to the cation or the anion, or dissolved in RTILs, providing a wide range of chemical solvents for CO{sub 2} capture. However, despite all of their promising features, RTILs do have drawbacks to use in CO{sub 2} separations, which have been overlooked as appropriate comparisons of RTILs to common organic solvents and polymers have not been reported. A thorough summary of the capabilities-and limitations-of imidazolium-based RTILs in CO{sub 2}-based separations with respect to a variety of materials is thus provided.

  6. Naphthalene-Functionalized, Photoluminescent Room Temperature Ionic Liquids Bearing Small Counterions.

    PubMed

    Zhu, Hongxia; Zhang, Geping; Chen, Mengjun; Zhou, Shengju; Li, Guihua; Wang, Xiaolin; Zhu, Qingzeng; Li, Hongguang; Hao, Jingcheng

    2016-04-25

    Obtaining π-conjugated room temperature ionic liquids (RTILs) is difficult because of the relatively strong π-π interaction among the π-moieties. Existing strategies by using bulky counterions greatly hindered further property optimization and potential applications of these intriguing functional fluids through simple ion exchange. Herein, four naphthalene-functionalized, π-conjugated RTILs with small counterions (Br(-) ) have been facilely synthesized with high yields. Our strategy is to attach branched alkyl chains to the cationic backbone of the target compounds (2 a-d), which effectively tune inter- and intramolecular interactions. Compounds 2 a-d have satisfactory thermal stability (up to 300 °C) and low melting points (<-19 °C). Rheological measurements revealed the fluid character of 2 a-d, whose viscosity decrease with the increase of the alkyl chain length and temperature. The presence of the π-conjugated naphthalene moiety imparts 2 a-d photoluminescent properties in bulk solutions. Moreover, the absence of strong π-π stacking among the naphthalene units in solvent-free states enables them to be used as a new generation of photoluminescent inks. PMID:26929087

  7. Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

    SciTech Connect

    Marin, T.; Shkrob, I.; Dietz, M.

    2011-04-14

    Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

  8. Effects of Room-Temperature Ionic Liquids on Zebra Mussels (Dreissena polymorpha)

    NASA Astrophysics Data System (ADS)

    Costello, D. M.; Bernot, R. J.; Lamberti, G. A.

    2005-05-01

    Zebra mussels (Dreissena polymorpha) are exotic bivalves that are widely distributed in eastern North America. We propose that this nuisance organism could serve as a model species for studies of aquatic toxicology. We tested zebra mussels response to room-temperature ionic liquids (ILs), which are being synthesized as environmentally friendly alternatives to volatile organic solvents. Volatile organic solvents contribute to atmospheric pollution and ozone depletion, whereas ILs are non-volatile and less harmful to the atmosphere. Although ILs would contribute significantly less to air pollution, little is known about their potential effects on aquatic ecosystems. In 72-hour toxicity tests, we determined the acute effects of three imidazolium-based ILs (1-butyl-3-methylimidazolium bromide (bmimBr), 1-hexyl-3-methylimidazolium bromide (hmimBr), and 1-octyl-3-methylimidazolium bromide (omimBr)) on the survival of zebra mussels. As alkyl chain length decreased, median lethal concentration (LC50) decreased from 1291 mg L-1 for bmimBr, to 105 mg L-1 for hmimBr, and 21.2 mg L-1 for omimBr. For bivalve mussels, the toxicities of these ILs are comparable to the toxicities of commonly used industrial solvents (e.g., toluene, benzene). This study presents a foundation for using zebra mussels in toxicity studies as well as possible models for less common Unionid mussels.

  9. Dielectric response of imidazolium-based room-temperature ionic liquids.

    PubMed

    Daguenet, Corinne; Dyson, Paul J; Krossing, Ingo; Oleinikova, Alla; Slattery, John; Wakai, Chihiro; Weingärtner, Hermann

    2006-06-29

    We have used microwave dielectric relaxation spectroscopy to study the picosecond dynamics of five low-viscosity, highly conductive room temperature ionic liquids based on 1-alkyl-3-methylimidazolium cations paired with the bis((trifluoromethyl)sulfonyl)imide anion. Up to 20 GHz the dielectric response is bimodal. The longest relaxation component at the time scale of several 100 ps reveals strongly nonexponential dynamics and correlates with the viscosity in a manner consistent with hydrodynamic predictions for the diffusive reorientation of dipolar ions. Methyl substitution at the C2 position destroys this correlation. The time constants of the weak second process at the 20 ps time scale are practically the same for each salt. This intermediate process seems to correlate with similar modes in optical Kerr effect spectra, but its physical origin is unclear. The missing high-frequency portion of the spectra indicates relaxation beyond the upper cutoff frequency of 20 GHz, presumably due to subpicosecond translational and librational displacements of ions in the cage of their counterions. There is no evidence for orientational relaxation of long-lived ion pairs. PMID:16800602

  10. Ideal gas solubilities and solubility selectivities in a binary mixture of room-temperature ionic liquids

    SciTech Connect

    Finotello Alexia; Bara Jason E.; Narayan Suguna; Campder Dean; Noble Richard D.

    2008-07-01

    This study focuses on the solubility behaviors of CO{sub 2}, CH{sub 4}, and N{sub 2} gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide ((C{sub 2}mim)(Tf{sub 2}N)) and l-ethyl-3-methylimidazolium tetrafluoroborate ((C{sub 2}mim)(BF{sub 4})) at 40{sup o}C and low pressures (about 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % (C{sub 2}mim)(BF{sub 4}) in (C{sub 2}-mim)(Tf2{sub N}). Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO{sub 2} with N{sub 2} or CH{sub 4} in pure (C{sub 2}mim)(BF4) can be enhanced by adding 5 mol% (C{sub 2}-mim)(Tf{sub 2}N).

  11. Crosslinking of polysaccharides in room temperature ionic liquids by ionizing radiation

    NASA Astrophysics Data System (ADS)

    Kimura, Atsushi; Nagasawa, Naotsugu; Shimada, Akihiko; Taguchi, Mitsumasa

    2016-07-01

    Crosslinking of polysaccharides in room temperature ionic liquids (RTILs) by ionizing radiation were investigated by the scavenging method, fluorescent and X-ray photoelectron spectroscopy (XPS) analysis. Radiation chemical yields of hydroxyl radicals inducing the crosslinking of cellulose were estimated with phenol as a scavenger, and increased with water content in 1-ethyl-3-methylimidazolium acetate (EMI-acetate). Cellulose gel was also produced in fluorescent carboxylate-based RTILs, 1,3-dibutylimidazolium acetate (DBI-acetate). Light emission from DBI-acetate in cellulose gel was observed and 20-nm red shifted at a maximum wavelength of 415 nm when excited at 323 nm. Expected elements of carbon and oxygen were detected in neat cellulose by XPS, while additional nitrogen was detected in radiation-crosslinked cellulose gel produced in EMI-acetate. These results indicate that RTILs is incorporated in the cellulose gel. Chitin gel was first obtained in 1-butyl-3-methyimidazolium chloride by γ-ray irradiations, and its gel fraction increased with the dose and reached 86% at 60 kGy.

  12. Effects of Room-Temperature Ionic Liquids on Freshwater Primary Producers

    NASA Astrophysics Data System (ADS)

    Kulacki, K. J.; Bernot, R. J.; Lamberti, G. A.; Lodge, D. M.

    2005-05-01

    Room-temperature ionic liquids (ILs) are non-volatile chemicals, which are presumed to be environmentally friendly because they pose no significant threat to air quality. However, the potential toxic effects of ILs on aquatic environments have not been studied, despite the likelihood of unintentional releases into streams and lakes during industrial applications. We studied the effects of ILs on the growth rates of the freshwater green algae Scenedesmus quadricauda and Chlamydomonas reinhardtii in 96-h bioassays. ILs with increasing alkyl chain lengths (from 1-butyl- to 1-hexyl- to 1-octyl-3-methylimidazolium bromide) were increasingly toxic to S. quadricauda (EC-50 values of 0.28 mg*L-1, 0.04 mg*L-1, and <0.005 mg*L-1 respectively). S. quadricauda growth rates decreased with increasing IL concentration across all treatments. Compared to controls, C. reinhardtii growth rates were higher at 200-800 mg*L-1 1-butyl-3-methylimidazolium bromide (bmimBr) treatments, but declined at 1600 mg*L-1 bmimBr. These results illustrate that different algal taxa can respond quite differently to potential chemical pollutants. Furthermore, by studying the effects of ILs on primary producers in concert with organisms from other trophic levels, we can develop hypotheses about how these effects may be felt throughout aquatic ecosystems.

  13. Correlation between hydrogen bond basicity and acetylene solubility in room temperature ionic liquids.

    PubMed

    Palgunadi, Jelliarko; Hong, Sung Yun; Lee, Jin Kyu; Lee, Hyunjoo; Lee, Sang Deuk; Cheong, Minserk; Kim, Hoon Sik

    2011-02-10

    Room temperature ionic liquids (RTILs) are proposed as the alternative solvents for the acetylene separation in ethylene generated from the naphtha cracking process. The solubility behavior of acetylene in RTILs was examined using a linear solvation energy relationship based on Kamlet-Taft solvent parameters including the hydrogen-bond acidity or donor ability (α), the hydrogen-bond basicity or acceptor ability (β), and the polarity/polarizability (π*). It is found that the solubility of acetylene linearly correlates with β value and is almost independent of α or π*. The solubility of acetylene in RTILs increases with increasing hydrogen-bond acceptor (HBA) ability of the anion, but is little affected by the nature of the cation. Quantum mechanical calculations demonstrate that the acidic proton of acetylene specifically forms hydrogen bond with a basic oxygen atom on the anion of a RTIL. On the other hand, although C-H···π interaction is plausible, all optimized structures indicate that the acidic protons on the cation do not specifically associate with the π cloud of acetylene. Thermodynamic analysis agrees well with the proposed correlation: the higher the β value of a RTIL is, the more negative the enthalpy of acetylene absorption in the RTIL is. PMID:21218815

  14. Picosecond time-resolved fluorescence study on solute-solvent interaction of 2-aminoquinoline in room-temperature ionic liquids: aromaticity of imidazolium-based ionic liquids.

    PubMed

    Iwata, Koichi; Kakita, Minoru; Hamaguchi, Hiro-o

    2007-05-10

    Time-resolved fluorescence spectra and fluorescence anisotropy decay of 2-aminoquinoline (2AQ) have been measured in eight room-temperature ionic liquids, including five imidazolium-based aromatic ionic liquids and three nonaromatic ionic liquids. The same experiments have also been carried out in several ordinary molecular liquids for comparison. The observed time-resolved fluorescence spectra indicate the formation of pi-pi aromatic complexes of 2AQ in some of the aromatic ionic liquids but not in the nonaromatic ionic liquids. The fluorescence anisotropy decay data show unusually slow rotational diffusion of 2AQ in the aromatic ionic liquids, suggesting the formation of solute-solvent complexes. The probe 2AQ molecule is likely to be incorporated in the possible local structure of ionic liquids, and hence the anisotropy decays only through the rotation of the whole local structure, making the apparent rotational diffusion of 2AQ slow. The rotational diffusion time decreases rapidly by adding a small amount of acetonitrile to the solution. This observation is interpreted in terms of the local structure formation in the aromatic ionic liquids and its destruction by acetonitrile. No unusual behavior upon addition of acetonitrile has been found for the nonaromatic ionic liquids. It is argued that the aromaticity of the imidazolium cation plays a key role in the local structure formation in imidazolium-based ionic liquids. PMID:17428083

  15. An electrochemical gas sensor based on paper supported room temperature ionic liquids.

    PubMed

    Dossi, Nicolò; Toniolo, Rosanna; Pizzariello, Andrea; Carrilho, Emanuel; Piccin, Evandro; Battiston, Simone; Bontempelli, Gino

    2012-01-01

    A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 μM; dynamic range: 2-200 μM, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: ±7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications. PMID:22076475

  16. Modeling stability and flexibility of α-Chymotrypsin in room temperature ionic liquids.

    PubMed

    Latif, Muhammad A M; Tejo, Bimo A; Abedikargiban, Roghayeh; Abdul Rahman, Mohd B; Micaêlo, Nuno M

    2014-01-01

    We investigate the structure and dynamics of α-Chymotrypsin in five room temperature ionic liquids (RTILs) sharing a common cation, hydrated with different water percentages (w/w) (weight of water over protein). Results from molecular dynamics simulations are correlated with experimental evidences from studies on the activity of enzymes in RTILs. α-Chymotrypsin protein structure is closer to its native crystallographic structure in RTILs than in aqueous environment. We show that the structural properties of α-Chymotrypsin were affected by the water concentration assayed in a typical bell-shaped profile, which is also frequently reported for organic solvents. The protein structure was more native like at 10-20% of water (w/w) for all RTILs except for [BMIM][Cl]. We found that the fluctuations of the main chain in [BMIM][BF4] and [BMIM][TfO] were not significantly affected by the increasing amount of water. However, we were able to show that the flexible regions were the ones more hydrated, indicating that water is responsible for the flexibility of the protein. The solvation of the enzyme in water-immiscible RTILs, such as [BMIM][PF6] and [BMIM][Tf2N] lead to higher enzyme flexibility at increased water content. Enzyme solvation by [BMIM][Cl] resulted in ion penetration in the core enzyme structure, causing incremented flexibility and destabilization at low water percentages. All RTILs stripped water molecules from the protein surface, following a similar behavior also found in organic solvents. Anions formed structured arrangements around the protein, which allowed non-stripped water molecules to localize on the protein surface. PMID:23844874

  17. Dispersion interactions in room-temperature ionic liquids: results from a non-empirical density functional.

    PubMed

    Kohanoff, Jorge; Pinilla, Carlos; Youngs, Tristan G A; Artacho, Emilio; Soler, José M

    2011-10-21

    The role of dispersion or van de Waals (VDW) interactions in imidazolium-based room-temperature ionic liquids is studied within the framework of density functional theory, using a recently developed non-empirical functional [M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004)], as efficiently implemented in the SIESTA code [G. Román-Pérez and J. M. Soler, Phys. Rev. Lett. 103, 096102 (2009)]. We present results for the equilibrium structure and lattice parameters of several crystalline phases, finding a general improvement with respect to both the local density (LDA) and the generalized gradient approximations (GGA). Similar to other systems characterized by VDW bonding, such as rare gas and benzene dimers as well as solid argon, equilibrium distances and volumes are consistently overestimated by ≈7%, compared to -11% within LDA and 11% within GGA. The intramolecular geometries are retained, while the intermolecular distances and orientations are significantly improved relative to LDA and GGA. The quality is superior to that achieved with tailor-made empirical VDW corrections ad hoc [M. G. Del Pópolo, C. Pinilla, and P. Ballone, J. Chem. Phys. 126, 144705 (2007)]. We also analyse the performance of an optimized version of this non-empirical functional, where the screening properties of the exchange have been tuned to reproduce high-level quantum chemical calculations [J. Klimes, D. Bowler, and A. Michaelides, J. Phys.: Condens. Matter 22, 074203 (2010)]. The results for solids are even better with volumes and geometries reproduced within 2% of experimental data. We provide some insight into the issue of polymorphism of [bmim][Cl] crystals, and we present results for the geometry and energetics of [bmim][Tf] and [mmim][Cl] neutral and charged clusters, which validate the use of empirical force fields. PMID:22029322

  18. Structure and dynamics of POPC bilayers in water solutions of room temperature ionic liquids

    SciTech Connect

    Benedetto, Antonio; Bingham, Richard J.; Ballone, Pietro

    2015-03-28

    Molecular dynamics simulations in the NPT ensemble have been carried out to investigate the effect of two room temperature ionic liquids (RTILs), on stacks of phospholipid bilayers in water. We consider RTIL compounds consisting of chloride ([bmim][Cl]) and hexafluorophosphate ([bmim][PF{sub 6}]) salts of the 1-buthyl-3-methylimidazolium ([bmim]{sup +}) cation, while the phospholipid bilayer is made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). Our investigations focus on structural and dynamical properties of phospholipid and water molecules that could be probed by inelastic and quasi-elastic neutron scattering measurements. The results confirm the fast incorporation of [bmim]{sup +} into the lipid phase already observed in previous simulations, driven by the Coulomb attraction of the cation for the most electronegative oxygens in the POPC head group and by sizeable dispersion forces binding the neutral hydrocarbon tails of [bmim]{sup +} and of POPC. The [bmim]{sup +} absorption into the bilayer favours the penetration of water into POPC, causes a slight but systematic thinning of the bilayer, and further stabilises hydrogen bonds at the lipid/water interface that already in pure samples (no RTIL) display a lifetime much longer than in bulk water. On the other hand, the effect of RTILs on the diffusion constant of POPC (D{sub POPC}) does not reveal a clearly identifiable trend, since D{sub POPC} increases upon addition of [bmim][Cl] and decreases in the [bmim][PF{sub 6}] case. Moreover, because of screening, the electrostatic signature of each bilayer is only moderately affected by the addition of RTIL ions in solution. The analysis of long wavelength fluctuations of the bilayers shows that RTIL sorption causes a general decrease of the lipid/water interfacial tension and bending rigidity, pointing to the destabilizing effect of RTILs on lipid bilayers.

  19. Ultrafast FRET in a room temperature ionic liquid microemulsion: a femtosecond excitation wavelength dependence study.

    PubMed

    Adhikari, Aniruddha; Das, Dibyendu Kumar; Sasmal, Dibyendu Kumar; Bhattacharyya, Kankan

    2009-04-23

    Fluorescence resonance energy transfer (FRET) from coumarin 480 (C480) to rhodamine 6G (R6G) is studied in a room temperature ionic liquid (RTIL) microemulsion by picosecond and femtosecond emission spectroscopy. The microemulsion is comprised of the RTIL 1-pentyl-3-methylimidazolium tetraflouroborate, [pmim][BF4], in TX-100/ benzene. We have studied the microemulsion with and without water. The time constants of FRET were obtained from the risetime of the acceptor (R6G) emission. In the RTIL microemulsion, FRET occurs on multiple time scales: 1, 250, and 3900 ps. In water containing RTIL microemulsion, the rise components are 1.5, 250, and 3900 ps. The 1 and 1.5 ps components are assigned to FRET at a close contact of donor and acceptor (RDA approximately 12 A). This occurs within the highly polar (RTIL/water) pool of the microemulsion. With increase in the excitation wavelength (lambdaex) from 375 to 435 nm, the relative contribution of the ultrafast component of FRET (1 ps) increases from 4% to 100% in the RTIL microemulsion and 12% to 100% in the water containing RTIL microemulsion. It is suggested that at lambdaex = 435 nm, mainly the highly polar RTIL pool is probed where FRET is very fast due to the close proximity of the donor and the acceptor. The very long 3900 ps (RDA approximately 45 A) component may arise from FRET from a donor in the outer periphery of the microemulsion to an acceptor in the polar RTIL pool. The 250 ps component (RDA approximately 29 A) is assigned to FRET from a donor inside the surfactant chains. PMID:19127996

  20. Synthesis and Characterization of Thiazolium-Based Room Temperature Ionic Liquids for Gas Separations

    SciTech Connect

    Hillesheim, PC; Mahurin, SM; Fulvio, PF; Yeary, JS; Oyola, Y; Jiang, DE; Dai, S

    2012-09-05

    A series of novel thiazolium-bis(triflamide) based ionic liquids has been synthesized and characterized. Physicochemical properties of the ionic liquids such as thermal stability, phase transitions, and infrared spectra were analyzed and compared to the imidazolium-based congeners. Several unique classes of ancillary substitutions are examined with respect to impacts on overall structure, in addition to their carbon dioxide absorption properties in supported ionic-liquid membranes for gas separation.

  1. High-Permeance Room-Temperature Ionic-Liquid-Based Membranes for CO2/N-2 Separation

    SciTech Connect

    Zhou, JS; Mok, MM; Cowan, MG; McDanel, WM; Carlisle, TK; Gin, DL; Noble, RD

    2014-12-24

    We have developed and fabricated thin-film composite (TFC) membranes with an active layer consisting of a room-temperature ionic liquid/polymerized (room-temperature ionic liquid) [i.e., (RTIL)/poly(RTIL)] composite material. The resulting membrane has a CO2 permeance of 6100 +/- 400 GPU (where 1 GPU = 10(-6) cm(3)/(cm(2) s cmHg)) and an ideal CO2/N-2 selectivity of 22 +/- 2. This represents a new membrane with state-of-the-art CO2 permeance and good CO2/N-2 selectivity. To our knowledge, this is the first example of a TFC gas separation membrane composed of an RTIL-containing active layer.

  2. Determination of water in room temperature ionic liquids by cathodic stripping voltammetry at a gold electrode.

    PubMed

    Zhao, Chuan; Bond, Alan M; Lu, Xunyu

    2012-03-20

    An electrochemical method based on cathodic stripping voltammetry at a gold electrode has been developed for the determination of water in ionic liquids. The technique has been applied to two aprotic ionic liquids, (1-butyl-3-ethylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate), and two protic ionic liquids, (bis(2-hydroxyethyl)ammonium acetate and triethylammonium acetate). When water is present in an ionic liquid, electrooxidation of a gold electrode forms gold oxides. Thus, application of an anodic potential scan or holding the potential of the electrode at a very positive value leads to accumulation of an oxide film. On applying a cathodic potential scan, a sensitive stripping peak is produced as a result of the reduction of gold oxide back to gold. The magnitude of the peak current generated from the stripping process is a function of the water concentration in an ionic liquid. The method requires no addition of reagents and can be used for the sensitive and in situ determination of water present in small volumes of ionic liquids. Importantly, the method allows the determination of water in the carboxylic acid-based ionic liquids, such as acetate-based protic ionic liquids, where the widely used Karl Fischer titration method suffering from an esterification side reaction which generates water as a side product. PMID:22372467

  3. Metal-air cell comprising an electrolyte with a room temperature ionic liquid and hygroscopic additive

    DOEpatents

    Friesen, Cody A.; Krishnan, Ramkumar; Tang, Toni; Wolfe, Derek

    2014-08-19

    An electrochemical cell comprising an electrolyte comprising water and a hydrophobic ionic liquid comprising positive ions and negative ions. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. A hydrophilic or hygroscopic additive modulates the hydrophobicity of the ionic liquid to maintain a concentration of the water in the electrolyte is between 0.001 mol % and 25 mol %.

  4. New Alkylether-Thiazolium Room-Temperature Ionic Liquid Lubricants: Surface Interactions and Tribological Performance.

    PubMed

    Espinosa, Tulia; Sanes, José; Bermúdez, María-Dolores

    2016-07-20

    The use of newly synthesized alkylether-thiazolium ionic liquids as lubricants is described for the first time. Two ionic liquids composed of a thiazolium cation and a bis(trifluoromethanesulfonyl)amide ([Th][Tf2N]) or dicyanamide ([Th][(NC)2N]) anion have been studied, and their tribological behavior has been compared with that of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Im][Tf2N]) in pin-on-disk tests using sapphire balls against AISI 52100 or AISI 316L steels. All ionic liquids show higher contact angles on AISI 316L steel than on AISI 52100, the lowest values found for ([Im][Tf2N]) on both steel surfaces. AISI 52100 shows similar friction coefficients for all lubricants, and negligible wear rates for the ionic liquids containing the bis(trifluoromethanesulfonyl)amide anion. Immersion tests show no corrosion of AISI 52100 in imidazolium or thiazolium bis(trifluoromethanesulfonyl)amide ionic liquids. AISI 316L shows similar friction coefficients for both bis(trifluoromethanesulfonyl)amide ionic liquids, but the lowest wear rate is obtained for [Th][Tf2N]. An increase in friction coefficient and wear rate is observed for thiazolium dicyanamide. This increase is related to a tribocorrosion process due to decomposition of the thiazolium cation. XPS shows the formation of iron sulfide on the wear track on AISI 316L after lubrication with thiazolium dicyanamide. No tribocorrosion processes take place for the [Tf2N] ionic liquids. PMID:27348604

  5. Differential solubility of ethylene and acetylene in room-temperature ionic liquids: a theoretical study.

    PubMed

    Zhao, Xu; Xing, Huabin; Yang, Qiwei; Li, Rulong; Su, Baogen; Bao, Zongbi; Yang, Yiwen; Ren, Qilong

    2012-04-01

    The room-temperature ionic liquids (RTILs) have potential in realizing the ethylene (C(2)H(4)) and acetylene (C(2)H(2)) separation and avoiding solvent loss and environmental pollution compared with traditional solvents. The interaction mechanisms between gases and RTILs are important for the exploration of new RTILs for gas separation; thus, they were studied by quantum chemical calculation and molecular dynamics simulation in this work. The optimized geometries were obtained for the complexes of C(2)H(4)/C(2)H(2) with anions (Tf(2)N(-), BF(4)(-), and OAc(-)), cation (bmim(+)), and their ion pairs, and the analysis for geometry, interaction energy, natural bond orbital (NBO), and atoms in molecules (AIM) was performed. The quantum chemical calculation results show that the hydrogen-bonding interaction between the gas molecule and anion is the dominant factor in determining the solubility of C(2)H(2) in RTILs. However, the hydrogen-bonding interaction, the p-π interaction in C(2)H(4)-anion, and the π-π interaction in C(2)H(4)-cation are weak and comparable, which all affect the solubility of C(2)H(4) in RTILs with comparable contribution. The calculated results for the distance of H(gas)···X (X = O or F in anions), the BSSE-corrected interaction energy, the electron density of H(gas)···X at the bond critical point (ρ(BCP)), and the relative second-order perturbation stabilization energy (E(2)) are consistent with the experimental data that C(2)H(2) is more soluble than C(2)H(4) in the same RTILs and the solubility of C(2)H(4) in RTILs has the following order: [bmim][Tf(2)N] > [bmim][OAc] > [bmim][BF(4)]. The calculated results also agree with the order of C(2)H(2) solubility in different RTILs that [bmim][OAc] > [bmim][BF(4)] > [bmim][Tf(2)N]. Furthermore, the calculation results indicate that there is strong C(2)H(2)-RTIL interaction, which cannot be negligible compared to the RTIL-RTIL interaction; thus, the regular solution theory is probably not

  6. Dynamics of water, methanol, and ethanol in a room temperature ionic liquid.

    PubMed

    Kramer, Patrick L; Giammanco, Chiara H; Fayer, Michael D

    2015-06-01

    The dynamics of a series of small molecule probes with increasing alkyl chain length: water, methanol, and ethanol, diluted to low concentration in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, was investigated with 2D infrared vibrational echo (2D IR) spectroscopy and polarization resolved pump-probe (PP) experiments on the deuterated hydroxyl (O-D) stretching mode of each of the solutes. The long timescale spectral diffusion observed by 2D IR, capturing complete loss of vibrational frequency correlation through structural fluctuation of the medium, shows a clear but not dramatic slowing as the probe alkyl chain length is increased: 23 ps for water, 28 ps for methanol, and 34 ps for ethanol. Although in each case, only a single population of hydroxyl oscillators contributes to the infrared line shapes, the isotropic pump-probe decays (normally caused by population relaxation) are markedly nonexponential at short times. The early time features correspond to the timescales of the fast spectral diffusion measured with 2D IR. These fast isotropic pump-probe decays are produced by unequal pumping of the OD absorption band to a nonequilibrium frequency dependent population distribution caused by significant non-Condon effects. Orientational correlation functions for these three systems, obtained from pump-probe anisotropy decays, display several periods of restricted angular motion (wobbling-in-a-cone) followed by complete orientational randomization. The cone half-angles, which characterize the angular potential, become larger as the experimental frequency moves to the blue. These results indicate weakening of the angular potential with decreasing hydrogen bond strength. The slowest components of the orientational anisotropy decays are frequency-independent and correspond to the complete orientational randomization of the solute molecule. These components slow appreciably with increasing chain length: 25 ps for water

  7. Dynamics of water, methanol, and ethanol in a room temperature ionic liquid

    NASA Astrophysics Data System (ADS)

    Kramer, Patrick L.; Giammanco, Chiara H.; Fayer, Michael D.

    2015-06-01

    The dynamics of a series of small molecule probes with increasing alkyl chain length: water, methanol, and ethanol, diluted to low concentration in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, was investigated with 2D infrared vibrational echo (2D IR) spectroscopy and polarization resolved pump-probe (PP) experiments on the deuterated hydroxyl (O-D) stretching mode of each of the solutes. The long timescale spectral diffusion observed by 2D IR, capturing complete loss of vibrational frequency correlation through structural fluctuation of the medium, shows a clear but not dramatic slowing as the probe alkyl chain length is increased: 23 ps for water, 28 ps for methanol, and 34 ps for ethanol. Although in each case, only a single population of hydroxyl oscillators contributes to the infrared line shapes, the isotropic pump-probe decays (normally caused by population relaxation) are markedly nonexponential at short times. The early time features correspond to the timescales of the fast spectral diffusion measured with 2D IR. These fast isotropic pump-probe decays are produced by unequal pumping of the OD absorption band to a nonequilibrium frequency dependent population distribution caused by significant non-Condon effects. Orientational correlation functions for these three systems, obtained from pump-probe anisotropy decays, display several periods of restricted angular motion (wobbling-in-a-cone) followed by complete orientational randomization. The cone half-angles, which characterize the angular potential, become larger as the experimental frequency moves to the blue. These results indicate weakening of the angular potential with decreasing hydrogen bond strength. The slowest components of the orientational anisotropy decays are frequency-independent and correspond to the complete orientational randomization of the solute molecule. These components slow appreciably with increasing chain length: 25 ps for water

  8. Dispersion interactions in room-temperature ionic liquids: Results from a non-empirical density functional

    NASA Astrophysics Data System (ADS)

    Kohanoff, Jorge; Pinilla, Carlos; Youngs, Tristan G. A.; Artacho, Emilio; Soler, José M.

    2011-10-01

    The role of dispersion or van de Waals (VDW) interactions in imidazolium-based room-temperature ionic liquids is studied within the framework of density functional theory, using a recently developed non-empirical functional [M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004), 10.1103/PhysRevLett.92.246401], as efficiently implemented in the SIESTA code [G. Román-Pérez and J. M. Soler, Phys. Rev. Lett. 103, 096102 (2009), 10.1103/PhysRevLett.103.096102]. We present results for the equilibrium structure and lattice parameters of several crystalline phases, finding a general improvement with respect to both the local density (LDA) and the generalized gradient approximations (GGA). Similar to other systems characterized by VDW bonding, such as rare gas and benzene dimers as well as solid argon, equilibrium distances and volumes are consistently overestimated by ≈7%, compared to -11% within LDA and 11% within GGA. The intramolecular geometries are retained, while the intermolecular distances and orientations are significantly improved relative to LDA and GGA. The quality is superior to that achieved with tailor-made empirical VDW corrections ad hoc [M. G. Del Pópolo, C. Pinilla, and P. Ballone, J. Chem. Phys. 126, 144705 (2007), 10.1063/1.2715571]. We also analyse the performance of an optimized version of this non-empirical functional, where the screening properties of the exchange have been tuned to reproduce high-level quantum chemical calculations [J. Klimes, D. Bowler, and A. Michaelides, J. Phys.: Condens. Matter 22, 074203 (2010), 10.1088/0953-8984/22/7/074203]. The results for solids are even better with volumes and geometries reproduced within 2% of experimental data. We provide some insight into the issue of polymorphism of [bmim][Cl] crystals, and we present results for the geometry and energetics of [bmim][Tf] and [mmim][Cl] neutral and charged clusters, which validate the use of empirical force

  9. 81929 - Fission-Product Separation Based on Room - Temperature Ionic Liquids

    SciTech Connect

    Robin D. Rogers

    2004-12-09

    This project has demonstrated that Sr2+ and Cs+ can be selectively extracted from aqueous solutions into ionic liquids using crown ethers and that unprecedented large distribution coefficients can be achieved for these fission products. The volume of secondary wastes can be significantly minimized with this new separation technology. Through the current EMSP funding, the solvent extraction technology based on ionic liquids has been shown to be viable and can potentially provide the most efficient separation of problematic fission products from high level wastes. The key results from the current funding period are the development of highly selective extraction process for cesium ions based on crown ethers and calixarenes, optimization of selectivities of extractants via systematic change of ionic liquids, and investigation of task-specific ionic liquids incorporating both complexant and solvent characteristics.

  10. Communication: Influence of nanophase segregation on ion transport in room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Griffin, Philip J.; Wang, Yangyang; Holt, Adam P.; Sokolov, Alexei P.

    2016-04-01

    We report measurements of the ionic conductivity, shear viscosity, and structural dynamics in a homologous series of quaternary ammonium ionic liquids (ILs) and a prototypical imidazolium-based IL over a wide range of temperatures down to the glass transition. We find that the ionic conductivity of these materials generally decreases, while the shear viscosity correspondingly increases, with increasing volume fraction of aliphatic side groups. Upon crossing an aliphatic volume fraction of ˜0.40, we observe a sharp, order-of-magnitude decrease in ionic conductivity and enhancement of viscosity, which coincides with the presence of long-lived, nanometer-sized alkyl aggregates. These strong changes in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.

  11. Fluorescence quenching of coumarin 153 by hydroxyl-functionalized room temperature ionic liquids.

    PubMed

    Li, Shuang; Yu, Anchi; Lu, Rong

    2016-08-01

    Steady-state absorption and fluorescence as well as time-resolved fluorescence of coumarin 151 (C151) and coumarin 153 (C153) were measured in hydroxyl-functionalized ionic liquids ([HOEmim][BF4] and [HOEmim][N(CN)2]) and in nonhydroxyl-functionalized ionic liquids ([Emim][BF4] and [Emim][N(CN)2]). Both the steady-state fluorescence and time-resolved fluorescence observations reveal that hydroxyl-functionalized ionic liquid quenches the fluorescence of C153 while the nonhydroxyl-functionalized ionic liquid does not. We also measured the time-resolved fluorescence anisotropy of C151 and C153 in both [HOEmim][BF4] and [Emim][BF4]. It is found that the ratio of the rotational relaxation lifetime of C153 in [HOEmim][BF4] with respect to that in [Emim][BF4] is about 15% larger than that of C151 in [HOEmim][BF4] with respect to that in [Emim][BF4], indicating extra interaction between C153 and [HOEmim][BF4] exists except the effect of the viscosity of ionic liquid. PMID:27153524

  12. Fluorescence quenching of coumarin 153 by hydroxyl-functionalized room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Li, Shuang; Yu, Anchi; Lu, Rong

    2016-08-01

    Steady-state absorption and fluorescence as well as time-resolved fluorescence of coumarin 151 (C151) and coumarin 153 (C153) were measured in hydroxyl-functionalized ionic liquids ([HOEmim][BF4] and [HOEmim][N(CN)2]) and in nonhydroxyl-functionalized ionic liquids ([Emim][BF4] and [Emim][N(CN)2]). Both the steady-state fluorescence and time-resolved fluorescence observations reveal that hydroxyl-functionalized ionic liquid quenches the fluorescence of C153 while the nonhydroxyl-functionalized ionic liquid does not. We also measured the time-resolved fluorescence anisotropy of C151 and C153 in both [HOEmim][BF4] and [Emim][BF4]. It is found that the ratio of the rotational relaxation lifetime of C153 in [HOEmim][BF4] with respect to that in [Emim][BF4] is about 15% larger than that of C151 in [HOEmim][BF4] with respect to that in [Emim][BF4], indicating extra interaction between C153 and [HOEmim][BF4] exists except the effect of the viscosity of ionic liquid.

  13. Theoretical and computational studies of renewable energy materials: Room temperature ionic liquids and proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Feng, Shulu

    2011-12-01

    Two kinds of renewable energy materials, room temperature ionic liquids (RTILs) and proton exchange membranes (PEMs), especially Nafion, are studied by computational and theoretical approaches. The ultimate purpose of the present research is to design novel materials to meet the future energy demands. To elucidate the effect of alkyl side chain length and anion on the structure and dynamics of the mixtures, molecular dynamics (MD) simulations of three RTILs/water mixtures at various water mole fractions: 1-butyl-3-methylimidazolium (BMIM+)/BF4-, 1-octyl-3-methylimidazolium (OMIM+)/BF4-, and OMIM +/Cl- are performed. Replacing the BMIM + cation with OMIM+ results in stronger aggregation of the cations as well as a slower diffusion of the anions, and replacing the BF4- anion with Cl- alters the water distribution at low water mole fractions and slows diffusion of the mixtures. Potential experimental manifestations of these behaviors in both cases are provided. Proton solvation properties and transport mechanisms are studied in hydrated Nafion, by using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. It is found that by stabilizing a more Zundel-like (H5O 2+) structure in the first solvation shells, the solvation of excess protons, as well as the proton hydration structure are both influenced by the sulfonate groups. Hydrate proton-related hydrogen bond networks are observed to be more stable than those with water alone. In order to characterize the nature of the proton transport (PT), diffusive motion, Arrhenius activation energies, and transport pathways are calculated and analyzed. Analysis of diffusive motion suggests that (1) a proton-hopping mechanism dominates the proton transport for the studied water loading levels and (2) there is an obvious degree of anti-correlation between the proton hopping and the vehicular transport. The activation energy drops rapidly with an increasing water content when the water loading level is smaller

  14. Electrodeposition of platinum nanoparticles in a room-temperature ionic liquid.

    PubMed

    Zhang, Da; Chang, Wan Cheng; Okajima, Takeyoshi; Ohsaka, Takeo

    2011-12-01

    The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger

  15. Metal electrodeposition and electron transfer studies of uranium compounds in room temperature ionic liquids.

    SciTech Connect

    Stoll, M. E.; Oldham, W. J.; Costa, D. A.

    2004-01-01

    Room temperature ionic liquids (RTIL's) comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and one of several anions such as PF{sub 6}{sup -}, BF{sub 4}{sup -}, or {sup -}N(SO{sub 2}CF{sub 3}){sub 2}, represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. Part of the intrigue with RTIL's stems from some of their inherent solvent properties including negligible vapor pressure, good conductivity, high chemical and thermal stability, and non-flammability. Additionally, a substantial number of RTIL's can be envisioned simply by combining different cation and anion pairs, thereby making them attractive for specific application needs. We are interested in learning more about the possible use of RTIL's within the nuclear industry. In this regard our research team has been exploring the electron transfer behavior of simple metal ions in addition to coordination and organometallic complexes in these novel solvents. Results from our research have also provided us with insight into the bonding interactions between our current anion of choice, bis(trifluoromethylsulfonyl)imide = NTf{sub 2}, and open coordination sites on actinide and transition metal fragments. This presentation will focus on recent results in two areas: the electrodeposition of electropositive metal ions from RTIL solutions and the electron transfer behavior for several uranium complexes. Details concerning the cathodic electrodeposition and anodic stripping of alkali metals (Na, K) from various working electrode surfaces (Pt, Au, W, Glassy Carbon) will be discussed. Figure 1 displays typical behavior for the electrodeposition of potassium metal from an RTIL containing potassium ions produced through the reaction of KH with H[NTf{sub 2}]. Our efforts with other metal ions, including our results to date with uranium electrodeposition, will be covered during the presentation. The electron transfer behavior for a number of uranium

  16. NOVEL FISSION PRODUCT SEPARATION BASED ON ROOM-TEMPERATURE IONIC LIQUIDS

    SciTech Connect

    Hussey, Charles L.

    2004-06-01

    The DoE/NE underground storage tanks at Hanford, SRS, and INEEL contain liquid wastes with high concentrations of radioactive species, mainly 137Cs and 90Sr. Because the other components of the liquid waste are mainly sodium nitrate and sodium hydroxide, most of this tank waste can be treated inexpensively as low-level waste if 137Cs and 90Sr can be selectively removed. Many ionophores (crown ether and calixarene compounds) have been synthesized for the purpose of selectively extracting Cs+ and Sr2+ from an aqueous phase into an immiscible organic phase. Recent studies conducted at ORNL1,2 reveal that hydrophobic ionic liquids might be better solvents for extracting metal ions from aqueous solutions with these ionophores than conventional immiscible organic solvents, such as benzene, toluene, and dichloromethane, because both Cs+ and Sr2+ exhibit larger distribution coefficients in the ionic liquids. In addition, the vapor pressures of these ionic liquids are insignificant. Thus, there is little or no vaporization loss of these solvents. Most of the ionic liquids under investigation are relatively nontoxic compared to the hydrocarbon solvents that they replace, classifying them as ''green'' solvents.

  17. Anomalous Freezing of Nano-Confined Water in Room-Temperature Ionic Liquid 1-Butyl-3-Methylimidazolium Nitrate.

    PubMed

    Abe, Hiroshi; Takekiyo, Takahiro; Yoshimura, Yukihiro; Saihara, Koji; Shimizu, Akio

    2016-04-18

    Non-crystal formation of ice is investigated by simultaneous X-ray diffraction and differential scanning calorimetry measurements upon cooling to -100 °C. At room temperature, size-tunable water confinement (≈20 Å size) in a room-temperature ionic liquid (RTIL, 1-butyl-3-methylimidazolium nitrate, [C4 mim][NO3 ]) exists in a water-rich region (70-90 mol % D2 O). The confined water (water pocket) is characterized by almost monodispersive size distribution. In [C4 mim][NO3 ]-x mol % D2 O (70

  18. Lithium-air batteries using hydrophobic room temperature ionic liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Kuboki, Takashi; Okuyama, Tetsuo; Ohsaki, Takahisa; Takami, Norio

    Lithium-air batteries using hydrophobic ionic liquid consisting of 1-alkyl-3-methyl imidazolium cation and perfluoroalkylsulfonyl imide anion were investigated. 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, which has high conductivity and prevents hydrolysis of the lithium anode, showed the best electrolyte performance. The cell worked for 56 days in air, and the cathode carbon materials showed high discharge capacity of 5360 mAh g -1. In addition to hydrophobic ionic liquids for use as electrolytes, various carbon materials for use as high-capacity cathodes were investigated.

  19. NOvel Fission Product Separation Based on Room-Temperature Ionic liquids

    SciTech Connect

    Hussey, Charles L.

    2005-11-13

    The effective extraction of Cs+ and Sr2+ into a relatively new and heretofore untested hydrophobic ionic liquid, tri-n-butylmethylammonium bis[(trifluoromethyl)sulfonyl]imide was demonstrated with calix[4]arene-bis(tert-octylbenzo-crown-6) and dicyclohexano-18-crown-6, respectively. The coordinated Cs+ and Sr2+ were subsequently removed from the ionic liquid extraction solvent by an electrochemical reduction process carried out at mercury electrodes. This process is non-destructive, permitting the ionic liquid and ionophores to be recycled. Although the process is based on mercury electrodes, this is a benefit rather than a detriment because the liquid mercury containing the Cs and Sr can be easily transported to another electrochemical cell where the Cs and Sr could be electrochemically recovered from the mercury amalgam and concentrated into a minimum volume of water or some other inexpensive solvent. This should facilitate the development of a suitable waste form for the extracted Cs+ and Sr2+. Thus, the feasibility of the proposed ionic liquid-based extraction cycle for the removal of 137Cs+ and 90Sr2+ from simulated aqueous tank waste was demonstrated.

  20. Solvation of [alpha]-hydroxydiphenylmethyl radical in room temperature ionic liquids studied by transient FT-EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kawai, Akio; Hidemori, Takehiro; Shibuya, Kazuhiko

    2005-10-01

    To understand solvation in room temperature ionic liquids (RTILs), an FT-EPR spectrum of α-hydroxydiphenylmethyl (HDPM) radical was measured in several RTILs of tert-alkylammonium or alkylimidazolium salts with anions of PF6-, BF4-, (CF 3SO 2) 2N -, CF3SO3-,WO42-, Cl - and Br -. The hyperfine coupling constant of the hydroxyl proton depends on Gutmann's donor number of the anions, while the constants of phenyl α-protons are essentially the same for these RTILs. This result suggests the electron donor character of anions is important in HDPM solvation in RTILs through the anion-OH group hydrogen-bond.

  1. FISSION-PRODUCT SEPARATION BASED ON ROOM-TEMPERATURE IONIC LIQUIDS

    EPA Science Inventory

    The objectives of this project are (a) to synthesize new ionic liquids tailored for the extractive separation of Cs + and Sr 2+; (b) to select optimum macrocyclic extractants through studies of complexation of fission products with macrocyclic extractants and transport in new ext...

  2. Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids

    SciTech Connect

    Bell, Jason R; Boll, Rose Ann; Dai, Sheng; Luo, Huimin

    2012-01-01

    The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficiencies and selectivities of Th-227/Ac-225 are also presented in this article.

  3. DETERMINATION OF HENRY'S LAW CONSTANTS FOR VOCS IN ROOM TEMPERATURE IONIC LIQUIDS

    EPA Science Inventory

    Ionic liquids (ILs) have been shown to be a newer medium for a wide variety of chemical reactions and are considered as the potential replacements for traditional volatile organic solvents. However, the separation and recovery of organic compounds from ILs has not been systematic...

  4. Novel Fission-Product Separation based on Room-Temperature Ionic Liquids

    SciTech Connect

    Rogers, Robin D.

    2004-12-31

    U.S. DOE's underground storage tanks at Hanford, SRS, and INEEL contain liquid wastes with high concentrations of radioactive cesium-137 and strontium-90. Because the primary chemical components of alkaline supernatants are sodium nitrate and sodium hydroxide, the majority of this could be disposed of as low level waste if radioactive cesium-137 and strontium- 90 could be selectively removed. The underlying goal of this project was to investigate the application of ionic liquids as novel solvents for new solvent extraction processes for separation of cesium-137 and strontium-90 from tank wastes. Ionic liquids are a distinct sub-set of liquids, comprising only of cations and anions they are proving to be increasingly interesting fluids for application in systems from electrochemistry to energetic materials, and are also rapidly establishing their promise as viable media for synthesis and separations operations. Properties including low melting points, electrochemical conductivity, wide liquid ranges, lack of vapor-pressure, and chemical tunability have encouraged researchers to explore the uses of ILs in place of volatile organic solvents. The most promising current developments arise from control of the unique combinations of chemical and physical properties characteristic of ionic liquids.

  5. Electrochemistry and spectroscopy of electrolytes and cathode materials in room-temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Ryan, David Martin

    were caused by the reduction of some other species of V(V) present in the acidic melts. New room temperature melts have been prepared by mixing Lewis acidic, VOCl3, with Lewis basic, EMIC. The new melts are dark red homogeneous liquids that are very conductive and easily reduced.

  6. Characterization of a novel intrinsic luminescent room-temperature ionic liquid based on [P6,6,6,14 ][ANS].

    PubMed

    Delgado, Joana M; Raymundo, Anabela; Vilarigues, Márcia; Branco, Luís C; Laia, César A T

    2015-01-01

    Intrinsically luminescent room-temperature ionic liquids (RTILs) can be prepared by combining a luminescent anion (more common) or cation with appropriate counter ions, rendering new luminescent soft materials. These RTILs are still new, and many of their photochemical properties are not well known. A novel intrinsic luminescent RTIL based on the 8-anilinonaphthalene-1-sulfonate ([ANS]) anion combined with the trihexyltetradecylphosphonium ([P6,6,6,14 ]) cation was prepared and characterized by spectroscopic techniques. Detailed photophysical studies highlight the influence of the ionic liquid environment on the ANS fluorescence, which together with rheological and (1) H NMR experiments illustrate the effects of both the viscosity and electrostatic interactions between the ions. This material is liquid at room temperature and possesses a glass transition temperature (Tg ) of 230.4 K. The fluorescence is not highly sensitive to factors such as temperature, but owing to its high viscosity, dynamic Stokes shift measurements reveal very slow components for the IL relaxation. PMID:25124894

  7. The dielectric response of room-temperature ionic liquids: effect of cation variation.

    PubMed

    Weingärtner, Hermann; Sasisanker, Padmanabhan; Daguenet, Corinne; Dyson, Paul J; Krossing, Ingo; Slattery, John M; Schubert, Thomas

    2007-05-10

    In continuation of recent work on the dielectric response of imidazolium-based ionic liquids (ILs) (J. Phys. Chem. B, 2006, 110, 12682), we report on the effect of cation variation on the frequency-dependent dielectric permittivity up to 20 GHz of ionic liquids. The salts are comprised of pyrrolidinium, pyridinium, tetraalkylammonium, and triethylsulfonium cations combined with the bis-((trifluoromethyl)sulfonyl)imide anion. The dielectric spectra resemble those observed for imidazolium salts with the same anion. In all cases, the major contribution results from a diffusive low-frequency response on the time scale of several 100 ps, which shows a broadly distributed kinetics similar to that of spatially heterogeneous states in supercooled and glassy systems rather than that observed in fluid systems. There is evidence for a weak secondary process near 10-20 ps. Perhaps the most interesting difference to imidazolium salts is founded in the missing portions of the spectra due to processes beyond the upper cutoff frequency of 20 GHz. These are lower than that observed for imidazolium-based salts and seem to vanish for tetraalkylammonium and triethylsulfonium salts. As for imidazolium salts, the extrapolated static dielectric constants are on the order of epsilon(S) congruent with 10-13, classifying these ILs as solvents of moderate polarity. PMID:17279790

  8. Preparation of nano/macroporous polycaprolactone microspheres for an injectable cell delivery system using room temperature ionic liquid and camphene.

    PubMed

    Kim, Seong Yeol; Hwang, Ji-Young; Shin, Ueon Sang

    2016-03-01

    The nano/macroporous polycaprolactone (PCL) microspheres with cell active surfaces were developed as an injectable cell delivery system. Room temperature ionic liquid (RTIL) and camphene were used as a liquid mold and a porogen, respectively. Various-sized spheres of 244-601μm with pores of various size and shape of 0.02-100μm, were formed depending on the camphene/RTIL ratio (0.8-2.6). To give cell activity, the surface of porous microspheres were further modified with nerve growth factors (NGF) containing gelatin to give a thin NGF/gelatin layer, to which the neural progenitor cells (PC-12) attached and extended their neurites on to the surface layers of the microspheres. The developed microspheres may be potentially applicable as a neuronal cell delivery scaffold for neuron tissue engineering. PMID:26641560

  9. Separation of carbon dioxide and sulfur dioxide gases using room-temperature ionic liquid (hmim)(Tf2N)

    SciTech Connect

    A. Yokozeki; Mark B. Shiflett

    2009-09-15

    To understand capturing and/or enhanced gaseous selectivity of industrial flue gases containing CO{sub 2} and SO{sub 2} using room-temperature ionic liquids, we have developed a ternary equation of state (EOS) model for a CO{sub 2}/SO{sub 2}/1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((hmim)(Tf2N)) system. The present model is based on a generic RK (Redlich-Kwong) EOS, with empirical binary interaction parameters of each binary system. These interaction parameters have been determined using our measured VLE (vapor-liquid-equilibrium) data for SO{sub 2}/(hmim)(Tf2N) and CO{sub 2}/(hmim)(Tf2N) and literature data for CO{sub 2}/SO{sub 2}. The validity of the present EOS has been checked by conducting ternary VLE experiments for the present system. With this EOS, isothermal ternary phase diagrams and solubility (VLE) behaviors have been calculated for various (T, P, and feed compositions) conditions. For large and equimolar CO{sub 2}/SO{sub 2} mole ratios, the gaseous selectivity is nearly independent of the amount of the ionic liquid addition. However, for small CO{sub 2}/SO{sub 2} mole ratios the addition of the ionic liquid significantly increases the selectivity. The strong absorption of CO{sub 2} and SO{sub 2} in this ionic liquid may be practical for the simultaneous capture of these acid gases. 39 refs., 8 figs., 4 tabs.

  10. Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

    PubMed

    Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

    2011-03-21

    Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. PMID:21394927

  11. Room temperature ionic liquid-mediated molecularly imprinted polymer monolith for the selective recognition of quinolones in pork samples.

    PubMed

    Sun, Xiangli; He, Jia; Cai, Guorui; Lin, Anqing; Zheng, Wenjie; Liu, Xuan; Chen, Langxing; He, Xiwen; Zhang, Yukui

    2010-12-01

    A novel molecularly imprinted polymer monolith was prepared by the room temperature ionic liquid-mediated in situ molecular imprinting technique, using norfloxacin (NOR) as the template, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker. The optimal synthesis conditions and recognition properties of NOR-imprinted monolithic column were investigated. The results indicated that the imprinted monoliths exhibited good ability of selective recognition against the template and its structural analog. Using the fabricated material as solid-phase extraction sorbent, a sample pre-treatment procedure of molecularly imprinted solid-phase extraction coupling with HPLC was developed for determination of trace quinolone residues in animal tissues samples. The recoveries ranging from 78.16 to 93.50% for eight quinolones antibiotics such as marbofloxacin, NOR, ciprofloxacin, danofloxacin, difloxacin, oxolinic acid, flumequine and enrofloxacin were obtained. PMID:21082676

  12. Electrochemistry of room temperature protic ionic liquids: a critical assessment for use as electrolytes in electrochemical applications.

    PubMed

    Lu, Xunyu; Burrell, Geoff; Separovic, Frances; Zhao, Chuan

    2012-08-01

    Ten room temperature protic ionic liquids (RTPILs) have been prepared from low-molecular-weight Brønsted acids and amines with high purity and minimal water content, and their electrochemical characteristics determined using cyclic, microelectrode, and rotating disk electrode voltammetries. Potential windows of the 10 RTPILs were established at glassy carbon, gold, and platinum electrodes, where the largest potential window is generally observed with glassy carbon electrodes. The two IUPAC recommended internal potential reference systems, ferrocene/ferrocenium and cobaltocenium/cobaltocene, were determined for the 10 RTPILs, and their merits as well as limitations are discussed. Other electrochemical properties such as mass transport and double layer capacitances were also investigated. The potential applications of these RTPILs as electrolytes for electrochemical energy devices were discussed, and two novel applications using PILs for metal deposition and water electrolysis were demonstrated. PMID:22784243

  13. Structure and dynamics of room temperature ionic liquids with bromide anion: results from 81Br NMR spectroscopy.

    PubMed

    Endo, Takatsugu; Imanari, Mamoru; Hidaka, Yuki; Seki, Hiroko; Nishikawa, Keiko; Sen, Sabyasachi

    2015-05-01

    We report the results of a comprehensive (81)Br NMR spectroscopic study of the structure and dynamics of two room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium bromide ([C(4)mim]Br) and 1-butyl-2,3-dimethylimidazolium bromide ([C(4)C(1)mim]Br), in both liquid and crystalline states. NMR parameters in the gas phase are also simulated for stable ion pairs using quantum chemical calculations. The combination of (81)Br spin-lattice and spin-spin relaxation measurements in the motionally narrowed region of the stable liquid state provides information on the correlation time of the translational motion of the cation. (81) Br quadrupolar coupling constants (C(Q)) of the two RTILs were estimated to be 6.22 and 6.52 MHz in the crystalline state which were reduced by nearly 50% in the liquid state, although in the gas phase, the values are higher and span the range of 7-53 MHz depending on ion pair structure. The C(Q) can be correlated with the distance between the cation-anion pairs in all the three states. The (81)Br C(Q) values of the bromide anion in the liquid state indicate the presence of some structural order in these RTILs, the degree of which decreases with increasing temperature. On the other hand, the ionicity of these RTILs is estimated from the combined knowledge of the isotropic chemical shift and the appropriate mean energy of the excited state. [C(4)C(1)mim]Br has higher ionicity than [C(4)mim]Br in the gas phase, while the situation is reverse for the liquid and the crystalline states. PMID:25783567

  14. Highly Efficient Extraction of Phenolic Compounds by Use of Magnetic Room Temperature Ionic Liquids for Environmental Remediation

    PubMed Central

    Deng, Ning; Li, Min; Zhao, Lijie; Lu, Chengfei; de Rooy, Sergio L.; Warner, Isiah M.

    2011-01-01

    A hydrophobic magnetic room temperature ionic liquid (MRTIL), trihexyltetradecylphosphonium tetrachloroferrate(III) ([3C6PC14][FeCl4]), was synthesized from trihexyltetradecylphosphonium chloride and FeCl3·6H2O. This MRTIL was investigated as a possible separation agent for solvent extraction of phenolic compounds from aqueous solution. Due to its strong paramagnetism, [3C6PC14][FeCl4] responds to an external neodymium magnet, which was employed in the design of a novel magnetic extraction technique. The conditions for extraction, including extraction time, volume ratio between MRTIL and aqueous phase, pH of aqueous solution, and structures of phenolic compounds were investigated and optimized. The magnetic extraction of phenols achieved equilibrium in 20 min and the phenolic compounds were found to have higher distribution ratios under acidic conditions. In addition, it was observed that phenols containing a greater number of chlorine or nitro substitutents exhibited higher distribution ratios. For example, the distribution ratio of phenol (DPh) was 107. In contrast, 3,5-dichlorophenol distribution ratio (D3,5-DCP) had a much higher value of 6372 under identical extraction conditions. When compared with four selected traditional non-magnetic room temperature ionic liquids, our [3C6PC14][FeCl4] exhibited significantly higher extraction efficiency under the same experimental conditions used in this work. Pentachlorophenol, a major component in the contaminated soil sample obtained from a superfund site, was successfully extracted and removed by use of [3C6PC14][FeCl4] with high extraction efficiency. Pentachlorophenol concentration was dramatically reduced from 7.8 μg.mL−1 to 0.2 μg.mL−1 after the magnetic extraction by use of [3C6PC14][FeCl4]. PMID:21783320

  15. Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions

    SciTech Connect

    Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

    2014-01-01

    We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (M. Z. Bazant, B. D. Storey, and A. A. Kornyshev, Phys. Rev. Lett., 106, 046102, 2011). Under very large charging currents, the cell potential shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface, allowing the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. Keywords: ionic

  16. Screening out the non-Arrhenius behaviour of nematic-isotropic transition by room temperature ionic liquid.

    PubMed

    Dan, K; Datta, A; Yoshida, Y; Saito, G; Yoshikawa, K; Roy, M

    2016-02-28

    Differential Scanning Calorimetry (DSC) and optical polarization microscopy of a mixture of the liquid crystalline material (N-(4-methoxybenzylidene)-4-butylaniline, MBBA) and a Fe-based room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate ([Emim](+) [FeCl4](-), EMIF) indicate a decrease in the nematic-isotropic (N-I) phase transition temperature (TNI) with an increase in EMIF concentration, explained by a proposed model of Coulomb "screening" of MBBA quadrupoles by the EMIF ions along with ionic "self screening." DSC studies of EMIF-MBBA and pure EMIF and comparison with pure MBBA results show that the major transitions in pure EMIF have Arrhenius behaviour, but more importantly the previously found convex Arrhenius behaviour of the pristine MBBA [K. Dan et al., Europhys. Lett. 108, 36007 (2014)] becomes Arrhenius in the mixture, indicating a conversion of the entropic N-I activation barrier to an enthalpic one. In presence of EMIF, a drastic decrease in the intensity of out-of-plane distortions of benzene rings in MBBA is found from Fourier transform infrared spectroscopy, consistent with significant reduction in the conformational states of MBBA. This suppression of large amplitude motion is again consistent with a Coulomb screening and gives a molecular basis for the entropic-to-enthalpic conversion of the N-I activation barrier. PMID:26931723

  17. Screening out the non-Arrhenius behaviour of nematic-isotropic transition by room temperature ionic liquid

    NASA Astrophysics Data System (ADS)

    Dan, K.; Datta, A.; Yoshida, Y.; Saito, G.; Yoshikawa, K.; Roy, M.

    2016-02-01

    Differential Scanning Calorimetry (DSC) and optical polarization microscopy of a mixture of the liquid crystalline material (N-(4-methoxybenzylidene)-4-butylaniline, MBBA) and a Fe-based room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate ([Emim]+ [FeCl4]-, EMIF) indicate a decrease in the nematic-isotropic (N-I) phase transition temperature (TNI) with an increase in EMIF concentration, explained by a proposed model of Coulomb "screening" of MBBA quadrupoles by the EMIF ions along with ionic "self screening." DSC studies of EMIF-MBBA and pure EMIF and comparison with pure MBBA results show that the major transitions in pure EMIF have Arrhenius behaviour, but more importantly the previously found convex Arrhenius behaviour of the pristine MBBA [K. Dan et al., Europhys. Lett. 108, 36007 (2014)] becomes Arrhenius in the mixture, indicating a conversion of the entropic N-I activation barrier to an enthalpic one. In presence of EMIF, a drastic decrease in the intensity of out-of-plane distortions of benzene rings in MBBA is found from Fourier transform infrared spectroscopy, consistent with significant reduction in the conformational states of MBBA. This suppression of large amplitude motion is again consistent with a Coulomb screening and gives a molecular basis for the entropic-to-enthalpic conversion of the N-I activation barrier.

  18. Green synthesis of polymer monoliths incorporated with carbon nanotubes in room temperature ionic liquid and deep eutectic solvents.

    PubMed

    Zhang, Li-Shun; Gao, Shu-Ping; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-07-01

    In this work, an efficient method to prepare polymer monoliths with incorporated carbon nanotubes in a mixture of room temperature ionic liquid and deep eutectic solvents was developed. With assistance of the binary green solvent, 1-butyl-3-methylimidazolium tetrafluoroborate and choline chloride/ethylene glycol, single-walled carbon nanotubes were dispersed successfully in pre-polymerization mixture without need of oxidative cutting of carbon nanotubes, which may allow depletion of the emission of volatile organic compounds into environment. The novel single-walled carbon nanotubes monolith was evaluated by capillary electrochromatography. Compared with the monolith made without single-walled carbon nanotubes, the monolith with the incorporation of single-walled carbon nanotubes exhibited high column efficiency (251,000plates/m) in the chromatographic separation. The morphology of the monolith can be tuned by the composition of mixture of ionic liquids and deep eutectic solvents to afford good column permeability and excellent separation ability for small molecules of alkyl phenones and alkyl benzenes. The results demonstrated that the method is a green strategy for the fabrication of multifunctional polymer monoliths. PMID:27154683

  19. Room temperature ionic liquids enhanced the speciation of Cr(VI) and Cr(III) by hollow fiber liquid phase microextraction combined with flame atomic absorption spectrometry.

    PubMed

    Zeng, Chujie; Lin, Yao; Zhou, Neng; Zheng, Jiaoting; Zhang, Wei

    2012-10-30

    A new method for the speciation of Cr(VI) and Cr(III) based on enhancement effect of room temperature ionic liquids (RTILs) for hollow fiber liquid phase microextraction (HF-LPME) combined with flame atomic absorption spectrometry (FAAS) was developed. Room temperature ionic liquids (RTILs) and diethyldithiocarbamate (DDTC) were used enhancement reagents and chelating reagent, respectively. The addition of room temperature ionic liquids led to 3.5 times improvement in the determination of Cr(VI). In this method, Cr(VI) reacts with DDTC yielding a hydrophobic complex, which is subsequently extracted into the lumen of hollow fiber, whereas Cr(III) is remained in aqueous solutions. The extraction organic phase was injected into FAAS for the determination of Cr(VI). Total Cr concentration was determined after oxidizing Cr(III) to Cr(VI) in the presence of KMnO(4) and using the extraction procedure mentioned above. Cr(III) was calculated by subtracting of Cr(VI) from the total Cr. Under optimized conditions, a detection limit of 0.7 ng mL(-1) and an enrichment factor of 175 were achieved. The relative standard deviation (RSD) was 4.9% for Cr(VI) (40 ng mL(-1), n=5). The proposed method was successfully applied to the speciation of chromium in natural water samples with satisfactory results. PMID:22981284

  20. Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions.

    PubMed

    Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

    2014-07-16

    We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement. PMID:24919471

  1. Supported phospholipid bilayer interaction with components found in typical room-temperature ionic liquids - a QCM-D and AFM study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Quartz crystal microbalance with dissipation monitoring and atomic force microscopy were combined to evaluate the defects created by room-temperature ionic liquid anion and cation in a supported phospholipid bilayer composed of Zwitterionic lipids on a silica surface. The cation 1-octyl-3-methyl im...

  2. High-pressure testing of heterogeneous charge transfer in a room-temperature ionic liquid: evidence for solvent dynamic control.

    PubMed

    Dolidze, Tina D; Khoshtariya, Dimitri E; Illner, Peter; Kulisiewicz, Leszek; Delgado, Antonio; van Eldik, Rudi

    2008-03-13

    We report the first application of a high-pressure electrochemical strategy to study heterogeneous charge transfer (CT) in a room-temperature ionic liquid, [BMIM][BTA]. High-pressure kinetic studies on electron exchange for two redox couples of different charge type, viz. [Fe(bipy)3]3+/2+ and [Fe(cp)2]+/0, at bare Au electrodes within the range of 0.1-150 MPa, revealed large positive volumes of activation that were found to be virtually the same for the two redox couples in terms of the CT rate constants and diffusion coefficients, despite the reactant's charge type. Independent viscosity (fluidity) studies at elevated pressure (up to 175 MPa), were also performed and revealed a pressure coefficient closely resembling the former ones. Complementary temperature-dependent kinetic studies within the range of 298-358 K also revealed the virtual similarity in activation enthalpies for the same kinetic and diffusion processes, as well as the viscosity of [BMIM][BTA]. A rigorous analysis of the complete variety of obtained results strongly indicates that dynamic (frictional) control of CT is operative by way of the full adiabatic mechanism. The contribution of the Franck-Condon term to the activation free energy of the kinetic process seems almost diminished because of the high value of electronic coupling and freezing out of the outer-sphere reorganization energy. Further analyses indicate that frictional control most probably takes place through slow translational modes (implying "minimal volume" cooperative dislocations) of constituent ions. This kind of motion seems further slowed down within the vicinity of the active site presumably located within the diffusive-like zone situated next to the compact (first) part of the metal/ionic liquid junction. PMID:18278899

  3. Room-temperature ionic liquid assisted fabrication of sensitive electrochemical immunosensor based on ordered macroporous gold film.

    PubMed

    Chen, Xiaojun; Zhou, Jinjun; Xuan, Jie; Yan, Wei; Jiang, Li-Ping; Zhu, Jun-Jie

    2010-10-01

    A novel label-free highly sensitive electrochemical impedance spectroscopy (EIS) immunosensor was fabricated based on the highly ordered macroporous gold film (HOMGF) in the presence of room-temperature ionic liquid (IL) for the detection of human Apolipoprotein B-100 (ApoB-100). The antibody of ApoB-100 (Ab) was adsorbed directly onto the HOMGF electrode surface and maintained its bioactivity. After the residual active sites at the electrode were passivated by BSA, the mixture of BMIm(+)BF(4)(-) and silica sol was dropped onto the electrode to entrap the adsorbed Ab and BSA molecules firmly. The addition of IL could prevent the inactivation of Ab by releasing alcohol during the sol-gel process, and the conductivity of the IL-gel membrane was increased. Of particular interest is the fact that the fabricated immunosensor could be used at 60 °C. This could be attributed to the interconnected porosity of the IL-gel membrane, which can prevent Ab from unfolding and losing its bioactivities. The immunosensor also exhibited a highly sensitive response to ApoB-100 with the lowest concentration of 5 fg mL(-1). The detection of ApoB-100 levels in five sera samples obtained from hospital showed acceptable accuracy with that using commercial immunonephelometry method. PMID:20694205

  4. Phase behavior and microstructure of microemulsions with a room-temperature ionic liquid as the polar phase.

    PubMed

    Atkin, Rob; Warr, Gregory G

    2007-08-01

    Microemulsions of nonionic alkyl oligoethyleneoxide (CiEj) surfactants, alkanes, and ethylammonium nitrate (EAN), a room-temperature ionic liquid, have been prepared and characterized. Studies of phase behavior reveal that EAN microemulsions have many features in common with corresponding aqueous systems, the primary difference being that higher surfactant concentrations and longer surfactant tailgroups are required to offset the decreased solvophobicity the surfactant molecules in EAN compared with water. The response of the EAN microemulsions to variation in the length of the alkane, surfactant headgroup, and surfactant tailgroup has been found to parallel that observed in aqueous systems in most instances. EAN microemulsions exhibit a single broad small-angle X-ray scattering peak, like aqueous systems. These are well described by the Teubner-Strey model. A lamellar phase was also observed for surfactants with longer tails at lower temperatures. The scattering peaks of both microemulsion and lamellar phases move to lower wave vector on increasing temperature. This is ascribed to a decrease in the interfacial area of the surfactant layer. Phase behavior, small-angle X-ray scattering, and conductivity experiments have allowed the weakly to strongly structured transition to be identified for EAN systems. PMID:17636975

  5. Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

    PubMed

    Gujar, R B; Ansari, S A; Verboom, W; Mohapatra, P K

    2016-05-27

    Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions. PMID:27130582

  6. Optical properties of irradiated imidazolium based room temperature ionic liquids: new microscopic insights into the radiation induced mutations.

    PubMed

    Guleria, Apurav; Singh, Ajay K; Adhikari, Soumyakanti

    2015-04-28

    Considering the future perspectives of room temperature ionic liquids (RTILs) in areas involving high radiation fields (such as the nuclear fuel cycle and space applications), it is essential to probe and have a microscopic understanding of the radiation induced perturbations in the molecular structures and the intrinsic bonding interactions existing in the ILs. Herein, a focused investigation concerning the photophysical behavior of post-irradiated FAP (fluoroalkyl phosphate) imidazolium ILs revealed considerable rearrangements and bonding realignments of the ionic moieties in the ILs on irradiation, however, their physicochemical properties do not change significantly even at high absorbed doses. Most interestingly, the well-established excitation wavelength dependent fluorescence (FL) behavior of the ILs was considerably perturbed on irradiation and this is attributed to the radiation induced decoupling of pre-existing different associated structures of ions, and the subsequent formation of oligomers and other species containing multiple bond order groups. This was further substantiated by vibrational studies, where peaks appearing in the range 1600-1800 cm(-1) indicated the formation of double bonded products. Furthermore, for the hydroxyl functionalized (in the alkyl side chain of the imidazolium cation) IL, a blue shift in the O-H stretching frequency was observed for the -OH group H-bonded to the FAP anion (νOH···[FAP](-)), while a red shift was observed for the H-bonded -OH groups in the cationic clusters. The FL lifetime values were found to increase with irradiation, which clearly indicates the enhancement in the rigidity level in the vicinity of the ions, thereby hindering the non-radiative decay processes. Such studies could contribute to the fundamental understanding of the radiation driven perturbations in the structure-property relationships, which eventually affect the radiolytic degradation pathways and the product distribution in RTILs. PMID

  7. Solvent systems for countercurrent chromatography: an aqueous two phase liquid system based on a room temperature ionic liquid.

    PubMed

    Ruiz-Angel, Maria Jose; Pino, Veronica; Carda-Broch, Samuel; Berthod, Alain

    2007-06-01

    A new aqueous two phase liquid system (ATPS) based on the ionic liquid 1-butyl-3-methyl imidazolium chloride (BMIM Cl), potassium dibasic phosphate (K(2)HPO(4)) and water was recently proposed in the literature. The full phase diagram of this ATPS was prepared and some tie lines were fully determined. It was compared to classical ATPSs based on polyethylene glycol with an average molecular mass of 1000 (PEG 1000) and 10,000 (PEG 10000) and K(2)HPO(4). Two countercurrent chromatography (CCC) columns, a hydrostatic Sanki and a J type hydrodynamic CCC columns were used to test the liquid phase retention of these ATPSs in all possible configurations. It was found that the BMIM Cl ATPS liquid phases were much easier to retain in the two CCC columns than the PEG 1000 ATPS phases. Using protein and alcohol solutes, it was established that the BMIM Cl ATPS has a polarity completely different from that of the PEG 1000 ATPS. For example, ovalbumin partitions equally between the two phases of the PEG 1000 ATPS (K(D)=1.4) when it is completely located in the BMIM Cl upper phase of the ionic liquid ATPS (K(D)=180). The discrimination factor of the ionic liquid system and its intrinsic hydrophobicity were respectively found three times higher and ten times lower than the respective values of the PEG 1000 ATPS. PMID:17166506

  8. The joint effects of room temperature ionic liquids and ordered media on fluorescence characteristics of estrogens in water and methanol

    NASA Astrophysics Data System (ADS)

    Wang, Huili; Duan, Ailian; Dahlgren, Randy A.; Li, Yanyan; Li, Changli; Wang, Wenwei; Zeng, Aibing; Wang, Xuedong

    2014-07-01

    This study investigated the steady-state and time-resolved fluorescence properties of 17α-ethinylestradiol (EE2) and 17β-estradiol (E2) in the presence of ordered media (β-cyclodextrins (β-CD) and cetyltrimethylammonium bromide (CTAB)). In addition, we analyzed the effects of four room temperature ionic liquids (RTILs) on the fluorescence intensities (FIs) of EE2/β-CD and E2/β-CD inclusion complexes in methanol. Both β-CD and CTAB enhanced the fluorescence of EE2 and E2. The FIs of EE2 and E2 with β-CD or CTAB in methanol were greater than those in water, possibly resulting from decreased oxygen-quenching in H2O molecules. β-CD and CTAB may form inclusion complexes with estrogen in both water and methanol. The inclusion ratio of the complex was 1:1 and the inclusion constant (K) values in water were greater than those in methanol. The fluorescence lifetimes were 2.50 and 4.13 ns for EE2 and 2.58 and 4.03 ns for E2 in aqueous solution and methanol, respectively. The changing trend of fluorescence lifetimes for EE2 and E2 in β-CD or CTAB was similar to the steady-state FIs. The four RTILs had a significant quenching effect on the FIs of EE2/β-CD and E2/β-CD, and the quenching process for EE2/β-CD and E2/β-CD by RTILs was demonstrated to be a dynamic quenching mechanism. Fluorescent data obtained from these complex systems provide a theoretical foundation for understanding the interaction mechanisms between ordered media and RTILs in the analysis of estrogens.

  9. Achievement of Prolonged Oxygen Detection in Room-Temperature Ionic Liquids on Mechanically Polished Platinum Screen-Printed Electrodes.

    PubMed

    Lee, Junqiao; Arrigan, Damien W M; Silvester, Debbie S

    2016-05-17

    The demonstration of prolonged amperometric detection of oxygen in room-temperature ionic liquids (RTILs) was achieved by the use of mechanical polishing to activate platinum screen-printed electrodes (Pt-SPEs). The RTILs studied were 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpyrr][NTf2]). It was found that voltammetry on polished Pt-SPEs exhibited less deterioration (in terms of voltammogram shapes, stability of peak currents, and appearance of contaminant peaks) from long-term consecutive cycling under 100% vol oxygen flow in both RTILs. The detection capability of these RTIL/Pt-SPE systems, initially subjected to long-term consecutive voltammetric cycling, was also investigated by cyclic voltammetry (CV) and long-term chronoamperometry (LTCA). Current versus concentration plots were linear on both unpolished and polished electrodes for 10-100% vol O2 (using CV) and 0.1-5% vol O2 (using LTCA). However, sensitivities and limits of detection (LODs) from CV were found to improve significantly on polished electrodes compared to unpolished electrodes, particularly in [C2mim][NTf2], but also moderately in [C4mpyrr][NTf2]. The lowest LODs (of ca. 0.1% vol O2) were found on polished SPEs using LTCA, with the most stable responses observed in [C4mpyrr][NTf2]. Calibration graphs could not be obtained on unpolished electrodes in both RTILs using LTCA. The results show that polishing markedly improves the analytical performances of Pt-SPEs for oxygen sensing in RTILs. The reusability of such disposable Pt-SPEs, after the surfaces had been experimentally fouled, was also demonstrated through the use of polishing. Mechanical polishing of Pt-SPE devices offers a viable approach to performance improvement for amperometric gas sensing. PMID:27063949

  10. Synergistic enhancement effect of room temperature ionic liquids for cloud point extraction combined with UV-vis spectrophotometric determination nickel in environmental samples

    NASA Astrophysics Data System (ADS)

    Zeng, Chujie; Xu, Xili; Zhou, Neng; Lin, Yao

    A new method based on enhancement effect of room temperature ionic liquids for cloud point extraction trace amounts of nickel combined with UV-vis spectrophotometric determination was developed. Room temperature ionic liquids (RTILs) and diethyldithiocarbamate (DDTC) were used enhancement reagent and chelating reagent, respectively. The addition of room temperature ionic liquids leads to 3.0 times improvement in the determination of nickel. The nonionic surfactant Triton X-100 was used as the extractant. When the temperature of the system was higher than the cloud point of Triton X-100, Ni-DTC complex was extracted into Triton X-100 and separation of the analyte from the matrix was achieved. Some parameters that influenced cloud point extraction and subsequent determination were evaluated in detail, such as the concentrations of RTILs, DDTC and Triton X-100; pH of sample solution, as well as interferences. Under optimized conditions, an enrichment factor of 72 could be obtained, and the detection limit (LOD) for Ni was 0.5 ng mL-1. Relative standard deviations for five replicate determinations of the standard solution containing 50 ng mL-1 Ni was 3.9%. The proposed method was successfully applied to the determination of nickel in certified reference materials with satisfactory results.

  11. High Power Electric Double-Layer Capacitors based on Room-Temperature Ionic Liquids and Nanostructured Carbons

    NASA Astrophysics Data System (ADS)

    Perez, Carlos R.

    The efficient storage of electrical energy constitutes both a fundamental challenge for 21st century science and an urgent requirement for the sustainability of our technological civilization. The push for cleaner renewable forms of energy production, such as solar and wind power, strongly depends on a concomitant development of suitable storage methods to pair with these intermittent sources, as well as for mobile applications, such as vehicles and personal electronics. In this regard, Electrochemical Double-Layer Capacitors (supercapacitors) represent a vibrant area of research due to their environmental friendliness, long lifetimes, high power capability, and relative underdevelopment when compared to electrochemical batteries. Currently supercapacitors have gravimetric energies one order of magnitude lower than similarly advanced batteries, while conversly enjoying a similar advantage over them in terms of power. The challenge is to increase the gravimentric energies and conserve the high power. On the material side, research focuses on highly porous supports and electrolytes, the critical components of supercapacitors. Through the use of electrolyte systems with a wider electrochemical stability window, as well as properly tailored carbon nanomaterials as electrodes, significant improvements in performance are possible. Room Temperature Ionic Liquids and Carbide-Derived Carbons are promising electrolytes and electrodes, respectively. RTILs have been shown to be stable at up to twice the voltage of organic solvent-salt systems currently employed in supercapacitors, and CDCs are tunable in pore structure, show good electrical conductivity, and superior demonstrated capability as electrode material. This work aims to better understand the interplay of electrode and electrolyte parameters, such as pore structure and ion size, in the ultimate performance of RTIL-based supercapacitors in terms of power, energy, and temperature of operation. For this purpose, carbon

  12. A higher performance dye-sensitized solar cell based on the modified PMII/EMIMBF4 binary room temperature ionic liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Wang, Wu-yang; Cao, Da-peng; Wang, Chao; Zhang, Xiang-yu; Mi, Bao-xiu; Gao, Zhi-qiang; Liang, Zhong-cheng

    2016-07-01

    Additives and iodine (I2) are used to modify the binary room temperature ionic liquid (RTIL) electrolyte to enhance the photovoltaic performance of dye-sensitized solar cells (DSSCs). The short-circuit current density ( J SC) of 17.89 mA/cm2, open circuit voltage ( V OC) of 0.71 V and fill factor ( FF) of 0.50 are achieved in the optimal device. An average photoelectric conversion efficiency ( PCE) of 6.35% is achieved by optimization, which is over two times larger than that of the parent device before optimization (2.06%), while the maximum PCE can reach up to 6.63%.

  13. Solvent and rotational relaxation of Coumarin-153 in a micellar solution of a room-temperature ionic liquid, 1-butyl-3-methylimidazolium octyl sulfate, in ethylammonium nitrate

    NASA Astrophysics Data System (ADS)

    Rao, Vishal Govind; Ghatak, Chiranjib; Pramanik, Rajib; Sarkar, Souravi; Sarkar, Nilmoni

    2010-10-01

    We have investigated the micelle formation by room-temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium octyl sulfate (bmimOs) with another RTIL, ethyl ammonium nitrate (EAN). In addition, the effect of micelle formation on the solvation and rotational relaxation dynamics have been observed using steady-state and picoseconds time-resolved spectroscopy. Both the solvent and rotational relaxations of Coumarin-153 are retarded in the micelle compared to that of neat EAN. The increase in average solvation time on going from neat EAN to bmimOs-EAN micelle is very small compared to the increase in solvation time on going from pure water to water containing micelle.

  14. Quantitative prediction of physical properties of imidazolium based room temperature ionic liquids through determination of condensed phase site charges: a refined force field.

    PubMed

    Mondal, Anirban; Balasubramanian, Sundaram

    2014-03-27

    Quantitative prediction of physical properties of room temperature ionic liquids through nonpolarizable force field based molecular dynamics simulations is a challenging task. The challenge lies in the fact that mean ion charges in the condensed phase can be less than unity due to polarization and charge transfer effects whose magnitude cannot be fully captured through quantum chemical calculations conducted in the gas phase. The present work employed the density-derived electrostatic and chemical (DDEC/c3) charge partitioning method to calculate site charges of ions using electronic charge densities obtained from periodic density functional theory (DFT) calculations of their crystalline phases. The total ion charges obtained thus range between -0.6e for chloride and -0.8e for the PF6 ion. The mean value of the ion charges obtained from DFT calculations of an ionic liquid closely matches that obtained from the corresponding crystal thus confirming the suitability of using crystal site charges in simulations of liquids. These partial charges were deployed within the well-established force field developed by Lopes et al., and consequently, parameters of its nonbonded and torsional interactions were refined to ensure that they reproduced quantum potential energy scans for ion pairs in the gas phase. The refined force field was employed in simulations of seven ionic liquids with six different anions. Nearly quantitative agreement with experimental measurements was obtained for the density, surface tension, enthalpy of vaporization, and ion diffusion coefficients. PMID:24605817

  15. A molecular dynamics computer simulation study of room-temperature ionic liquids. I. Equilibrium solvation structure and free energetics

    NASA Astrophysics Data System (ADS)

    Shim, Y.; Choi, M. Y.; Kim, Hyung J.

    2005-01-01

    Solvation in 1-ethyl-3-methylmidazolium chloride and in 1-ethyl-3-methylimidazolium hexafluorophosphate near equilibrium is investigated via molecular dynamics computer simulations with diatomic and benzenelike molecules employed as probe solutes. It is found that electrostriction plays an important role in both solvation structure and free energetics. The angular and radial distributions of cations and anions become more structured and their densities near the solute become enhanced as the solute charge separation grows. Due to the enhancement in structural rigidity induced by electrostriction, the force constant associated with solvent configuration fluctuations relevant to charge shift and transfer processes is also found to increase. The effective polarity and reorganization free energies of these ionic liquids are analyzed and compared with those of highly polar acetonitrile. Their screening behavior of electric charges is also investigated.

  16. Novel method of room temperature ionic liquid assisted Fe{sub 3}O{sub 4} nanocubes and nanoflakes synthesis

    SciTech Connect

    Ramalakshmi, M.; Shakkthivel, P.; Sundrarajan, M.; Chen, S.M.

    2013-08-01

    Graphical abstract: - Highlights: • First time [Bmim][TfO] IL is used for the Fe{sub 3}O{sub 4} nanoparticle synthesis. • Novel method tunes Fe{sub 3}O{sub 4} nanocubes and nanoflakes forms influenced by the base and IL. • Fe{sub 3}O{sub 4} oxidized topotactically into γ-Fe{sub 2}O{sub 3} nanoparticles by annealing and base. • Uniform morphology with average size of 33 nm negligible superstructure are formed. • Ms values are characterized by thin layer of γ-Fe{sub 2}O{sub 3} on the nanoparticle surface. - Abstract: For the first time, the nanomagnetite superparamagnetic particles are successfully synthesized by precipitation method using 1-n-butyl-3-methylimidazolium trifluoromethane sulfonate [Bmim][TfO] ionic liquid medium/surfactant. The obtained Fe{sub 3}O{sub 4} particles are nanocubes and nanoflakes and this formation is influenced by the base concentration and anisotropic circumstances produced by the ionic liquid and their size varies from 20 nm to 150 × 300 nm (width × length). The synthesized magnetite nanoparticles are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, Field emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM) and Vibrating sample magnetometer (VSM) studies. The results show that the core of the Fe{sub 3}O{sub 4} nanoparticles is surrounded by a thin layer of γ-Fe{sub 2}O{sub 3} by topotactical partial oxidation, which is remarkably proceed with the subsequent calcination. The magnetite nanocubes have high saturation magnetization value and exhibit superparamagnetic hysteresis loop.

  17. Studies on the nuances of the electrochemically induced room temperature isomerization of cis-stilbene in acetonitrile and ionic liquids.

    PubMed

    Abdul-Rahim, Omar; Simonov, Alexandr N; Boas, John F; Rüther, Thomas; Collins, David J; Perlmutter, Patrick; Bond, Alan M

    2014-03-20

    Electrochemical reduction of cis-stilbene occurs by two well-resolved one-electron reduction steps in acetonitrile with (n-Bu)4NPF6 as the supporting electrolyte and in N-butyl-N-methylpyrrolidinium (Pyrr1,4(+)) and (trimethylamine)(dimethylethylamine)-dihydroborate bis(trifluoromethylsulfonyl)amide (NTf2(-)) ionic liquids (ILs). Mechanistic details of the electroreduction have been probed by dc and Fourier transformed ac voltammetry, simulation of the voltammetry, bulk electrolysis, and EPR spectroscopy. The first one-electron reduction induces fast cis to trans isomerization in CH3CN and ILs, most likely occurring via disproportionation of cis-stilbene radical anions and fast transformation of the cis-dianion to the trans-configuration. The second reduction process is chemically irreversible in CH3CN due to protonation of the dianion but chemically reversible in highly aprotic ILs under high cis-stilbene concentration conditions. Increase of the (n-Bu)4NPF6 supporting electrolyte concentration (0.01-1.0 M) in CH3CN induces substantial positive shifts in the potentials for reduction of cis-stilbene, consistent with strong ion pairing of the anion radical and dianion with (n-Bu)4N(+). However, protection by ion pairing against protonation of the stilbene dianions or electrochemically induced cis-trans-stilbene isomerization is not achieved. Differences in electrode kinetics and reversible potentials for cis-stilbene(0/•-) and trans-stilbene(0/•-) processes are less pronounced in the Pyrr1,4-NTf2 ionic liquid than in the molecular solvent acetonitrile. PMID:24558952

  18. Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

    DOE PAGESBeta

    Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; Meisner, Roberta Ann; Meyer, III, Harry M.; Luo, Huimin; Delmau, Laetitia Helene; Dai, Sheng; Moyer, Bruce A

    2013-11-11

    Our study demonstrates a direct electrodeposition of UO2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO2(NTf2)2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM+NTf2–). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. The UO2deposit was characterized by powder X-ray diffraction (XRD)more » and X-ray photoelectron spectroscopy (XPS).« less

  19. Communication: Collective dynamics of room-temperature ionic liquids and their Li ion solutions studied by high-resolution inelastic X-ray scattering

    NASA Astrophysics Data System (ADS)

    Fujii, Kenta; Shibayama, Mitsuhiro; Yamaguchi, Tsuyoshi; Yoshida, Koji; Yamaguchi, Toshio; Seki, Shiro; Uchiyama, Hiroshi; Baron, Alfred Q. R.; Umebayashi, Yasuhiro

    2013-04-01

    High-resolution inelastic X-ray scattering (IXS) measurements were performed for room-temperature ionic liquids (ILs) of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide and bis(fluorosulfonyl)amide, [C2mIm+][TFSA-] and [C2mIm+][FSA-], respectively, at ambient temperature. The observed spectra as a function of Q of 1.4-6 nm-1 can be ascribed to quasi-elastic and inelastic scatterings, so that they are well represented with the fitting by using the Lorentz and the damped harmonic oscillator model functions to yield the dynamic structure factors. It was found in the intermediate scattering function, F(Q, t) that both ILs show the relaxation at t < 10 ps. The IXS measurements were also made on [C2mIm+][TFSA-] and [C2mIm+][FSA-] solutions dissolving Li salt. It is suggested that the adding of Li salt to IL significantly prolongs the relaxation time.

  20. Corrosion of Ni in 1-butyl-1-methyl-pyrrolidinium bis (trifluoromethylsulfonyl) amide room-temperature ionic liquid: an in situ X-ray imaging and spectromicroscopy study.

    PubMed

    Bozzini, Benedetto; Gianoncelli, Alessandra; Kaulich, Burkhard; Kiskinova, Maya; Mele, Claudio; Prasciolu, Mauro

    2011-05-01

    This paper reports a pioneering application of soft X-ray scanning transmission microscopy (STXM), combined with micro-spot X-ray absorption spectroscopy (XAS) and X-ray fluorescence spectroscopy (XRF), for the investigation of the corrosion of metal electrodes in contact with room-temperature ionic liquids (RTIL). Using an open electrochemical cell in vacuo we explore some fundamental aspects of the aggressiveness of the 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP][TFSA]) RTIL towards Ni under in situ electrochemical polarisation. The possibility of imaging electrochemically-induced morphological features in conjunction with micro-XAS and XRF spectroscopies has provided unprecedented details regarding the space distribution and chemical state of corrosion products. PMID:21437296

  1. Chemical structure of extracted copper from scrap Cu/ITO thin films in a room temperature ionic liquid containing iodine/iodide

    NASA Astrophysics Data System (ADS)

    Huang, Hsin-Liang; Huang, Hsin-Hung; Wei, Yu Jhe

    2016-05-01

    A RTIL (room temperature ionic liquid) containing iodine/iodide (RTIL-I) was studied to determine its coated copper extraction efficiency on the surface of scrap Cu/indium tin oxide (ITO) thin films. According to the X-ray absorption near edge structural spectra and transmission electron microscopy observations, about 95% of Cu with the size of 80 nm was stripped from scrap Cu/ITO thin film into the RTIL-I and then formed 90 nm of α-CuI and CuI2- within 30 min at 298 K. The 31P NMR (nuclear magnetic resonance) spectra suggests [PF6]- of the RTIL-I may enhance the extraction of nanoparticles into the RTIL-I.

  2. Room temperature ionic liquids: new GC stationary phases with a novel selectivity for flavor and fragrance analyses.

    PubMed

    Cagliero, Cecilia; Bicchi, Carlo; Cordero, Chiara; Liberto, Erica; Sgorbini, Barbara; Rubiolo, Patrizia

    2012-12-14

    Ionic liquids (ILs) are of great interest as moderately polar to polar stationary phases for GC, because their selectivity differs markedly from that of conventionally used phases. In the flavor, fragrance and essential oil fields, analysts often deal with complex mixtures of compounds having similar structural and physical characteristics (e.g., mono- and sesquiterpenoids), therefore requiring an interactive combination between chromatographic and mass spectral data for correct identification. New GC stationary phases with different selectivity must therefore be continually tested. Performance and evolution over time of commercially available IL columns versus those commonly used in these fields are here evaluated, mainly in view of their routine use. Chromatographic and separative properties (efficiency, separation capability, inertness and/or activity) of commercially available IL columns were compared to those of columns coated with 5% phenyl-95% methylpolysiloxane, 14% cyanopropyl-86% polysiloxane, and polyethylene glycol, on different complexity samples, including standard mixtures of volatile suspected allergens and pesticides, and cornmint and vetiver essential oils. The results show that IL columns can successfully be used for a wide range of applications characteristic of these fields, mainly because of their unusual selectivity, in particular when separations based on functional groups are required. Moreover, the latest generation of IL columns (IL61 and IL60) presents chromatographic performance comparable to or only slightly lower than that of the conventional columns routinely used in these fields. PMID:23122273

  3. A kinetic study of the reaction between N,N-dimethyl-p-toluidine and its electrogenerated radical cation in a room temperature ionic liquid.

    PubMed

    Evans, Russell G; Compton, Richard G

    2006-02-13

    The reaction between N,N-dimethyl-p-toluidine (DMT) and the radical cation generated through its one-electron oxidation has been studied electrochemically in the room temperature ionic liquid N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [Py14][NTf2]. Kinetic information obtained as linear sweep and cyclic voltammetry collected at 5 microm, 10 microm and 0.3 mm diameter platinum disk electrodes over a range of initial substrate concentrations and scan rates spanning five orders of magnitude was complemented by chronoamperometric measurements designed to probe the rate of diffusion. At the fastest scan rates the homogeneous reactions following the initial electron transfer were effectively out-run, facilitating an assessment of the electrode kinetics using DIGISIM and a validated Nicholson's method. Through digital simulation the voltammetry was then shown to be consistent with a mechanism established for the same reaction in acetonitrile, involving dimerisation of the DMT radicals following an initial and rate-determining proton transfer step. After careful consideration of all parameters, a bimolecular rate constant of (3.4 +/- 1.1) x 10(2) dm3 mol(-1) s(-1) was deduced by fitting the data. This was compared to the equivalent value for acetonitrile and, in light of this, the implications on the viability of ionic liquids for use as alternative mainstream solvents briefly assessed. PMID:16463338

  4. Protein Crystallization Using Room Temperature Ionic Fluids

    NASA Technical Reports Server (NTRS)

    Pusey, Marc L.; Paley, Mark Steve; Turner, Megan B.; Rogers, Robin D.

    2006-01-01

    The ionic liquids (ILs) 1-butyl-3-methylimidizolium chloride (C4mim-C1), 1-butyl-3- methylimidizolium diethyleneglycol monomethylethersulfate ([C4mim]DEMGS), and 1-butyl-1 -methylpyrollidinium dihydrogenphosphate ([p1,4]dhp) were tested for their effects on the crystallization of the proteins canavalin, beta-lactoglobulin B, xylanase, and glucose isomerase, using a standard high throughput screen. The crystallization experiments were set up with the ILs added to the protein solutions at 0.2 and 0.4 M final concentrations. Crystallization droplets were set up at three proteixprecipitant ratios (1:1, 2:1, and 4:l), which served to progressively dilute the effects of the screen components while increasing the equilibrium protein and IL concentrations. Crystals were obtained for all four proteins at a number of conditions where they were not obtained from the IL-free control experiment. Over half of the protein-IL combinations tested had more successful outcomes than negative, where the IL-free crystallization was better than the corresponding IL-containing outcome, relative to the control. One of the most common causes of a negative outcome was solubilization of the protein by the IL, resulting in a clear drop. In one instance, we were able to use the IL-induced solubilizing to obtain beta-lactoglobulin B crystals from conditions that gave precipitated protein in the absence of IL. The results suggest that it may be feasible to develop ILs specifically for the task of macromolecule crystallization.

  5. Part I. Synthesis and characterization of C2 substituted imidazolium room temperature ionic liquids. Part II. Survey and analysis of organic chemistry textbooks

    NASA Astrophysics Data System (ADS)

    Ennis, Elliot G.

    Part I. Among room temperature ionic liquids (RTILs), those derived from the imidazolium cation are the most common. RTILs have generally been viewed solely as solvents, but they are able to participate in certain types of reactions, particularly due to the relatively high acidity at the imidazolium C2. Deprotonation affords N-heterocyclic carbenes (NHCs), which can cause unwanted side reactions. Consequently, the major limitation of imidazolium RTILs is that they cannot be used as solvents in highly basic reactions such as the Baylis-Hillman and Grignard reactions. This work reveals a convenient route for the preparation of C2-substituted imidazolium ionic liquids. This method involves the alkylation of N-heterocyclic carbenes, which are readily generated from the C2-unsubstituted imidazolium ionic liquids. It works well for nonfunctionalized alkyl chlorides and less well for alkyl bromides and iodides, likely due to competing elimination reactions. The resulting C2-substituted salts can be transformed into ionic liquids via standard anion metathesis reactions. Part II. Recent advances in media and the increasingly encyclopedic nature of traditional textbooks have made their role in college classes uncertain. In an effort to discover what is really being taught in organic chemistry courses across the US, a survey of organic chemistry professors in all 50 states was conducted to determine what material is covered in their organic chemistry courses for science majors. Survey Monkey, an online survey program, was used to construct a short 10-item survey which was sent to organic chemistry professors at various types of institutions across the nation. We sent out 2417 surveys and received 489 responses. The results of this survey revealed what topics the professors believe is core material and what they feel is extraneous. Additionally, this research identifies the things these professors would like to see changed in the organic chemistry texts. From the open

  6. NMR Study on Ion Dynamics and Phase Behavior of a Piperidinium-Based Room-Temperature Ionic Liquid: 1-Butyl-1-methylpiperidinium Bis(fluorosulfonyl)amide.

    PubMed

    Shimizu, Yuichi; Wachi, Yuto; Fujii, Kozo; Imanari, Mamoru; Nishikawa, Keiko

    2016-06-30

    By use of pulse NMR methods, the temperature dependences of the longitudinal and transverse relaxation times for (1)H and (19)F were measured for the three phases of 1-butyl-1-methylpiperidinium bis(fluorosulfonyl)amide ([Pip1,4][FSA]), i.e., liquid or supercooled liquid, Cryst-α, and Cryst-β, to investigate the ion dynamics and phase behavior related to the dynamics. Since the cations and anions in the room-temperature ionic liquid have (1)H and (19)F nuclei, respectively, the dynamics of the [Pip1,4] cation and [FSA] anion can be independently observed and the relation between them can be evaluated. The relevant local motions of the ions are fluctuational motion around the chair form of the piperidinium ring, libration or rotation of the alkyl groups, and libration or rotation of the SO2F groups around the N-S axes. Each phase preferentially exhibits these motions. In the Cryst-β phase, it is thought that O atoms in the SO2F groups form strong hydrogen bonds with the H atoms in the piperidinium ring. As a result, the motions of the SO2F groups and the piperidinium ring are restricted. In the liquid or supercooled liquid states and Cryst-α phase, the motion of the anion is more significant than that of the cation and the former works as a trigger for phase changes. Particularly, the motion of the SO2F groups in the Cryst-α phase becomes very significant with rising temperature and is directly related to the melting phase transition. PMID:27281062

  7. Easily Accessible Rare-Earth-Containing Phosphonium Room-Temperature Ionic Liquids: EXAFS, Luminescence, and Magnetic Properties.

    PubMed

    Alvarez-Vicente, Jorge; Dandil, Sahra; Banerjee, Dipanjan; Gunaratne, H Q Nimal; Gray, Suzanne; Felton, Solveig; Srinivasan, Geetha; Kaczmarek, Anna M; Van Deun, Rik; Nockemann, Peter

    2016-06-16

    A range of liquid rare earth chlorometallate complexes with the alkyl-phosphonium cation, [P666 14](+), has been synthesized and characterized. EXAFS confirmed the predominant liquid-state speciation of the [LnCl6](3-) ion in the series with Ln = Nd, Eu, Dy. The crystal structure of the shorter-alkyl-chain cation analogue [P4444](+) has been determined and exhibits a very large unit cell. The luminescence properties, with visible-light emissions of the liquid Tb, Eu, Pr, and Sm and the NIR emissions for the Nd and Er compounds, were determined. The effective magnetic moments were measured and fitted for the Nd, Tb, Ho, Dy, Gd, and Er samples. PMID:27203286

  8. Electrochemistry and spectroelectrochemistry of 1,4-dinitrobenzene in acetonitrile and room-temperature ionic liquids: ion-pairing effects in mixed solvents.

    PubMed

    Atifi, Abderrahman; Ryan, Michael D

    2014-07-01

    Room-temperature ionic liquids (RTILs) have been shown to have a significant effect on the redox potentials of compounds such as 1,4-dinitrobenzene (DNB), which can be reduced in two one-electron steps. The most noticeable effect is that the two one-electron waves in acetonitrile collapsed to a single two-electron wave in a RTIL such as butylmethyl imidazolium-BF4 (BMImBF4). In order to probe this effect over a wider range of mixed-molecular-solvent/RTIL solutions, the reduction process was studied using UV-vis spectroelectrochemistry. With the use of spectroelectrochemistry, it was possible to calculate readily the difference in E°'s between the first and second electron transfer (ΔE12° = E1° - E2°) even when the two one-electron waves collapsed into a single two-electron wave. The spectra of the radical anion and dianion in BMImPF6 were obtained using evolving factor analysis (EFA). Using these spectra, the concentrations of DNB, DNB(-•), and DNB(2-) were calculated, and from these concentrations, the ΔE12° values were calculated. Significant differences were observed when the bis(trifluoromethylsulfonyl)imide (NTf2) anion replaced the PF6(-) anion, leading to an irreversible reduction of DNB in BMImNTf2. The results were consistent with the protonation of DNB(2-), most likely by an ion pair between DNB(2-) and BMIm(+), which has been proposed by Minami and Fry. The differences in reactivity between the PF6(-) and NTf2(-) ionic liquids were interpreted in terms of the tight versus loose ion pairing in RTILs. The results indicated that nanostructural domains of RTILs were present in a mixed-solvent system. PMID:24884098

  9. Structure and stability of phospholipid bilayers hydrated by a room-temperature ionic liquid/water solution: a neutron reflectometry study.

    PubMed

    Benedetto, Antonio; Heinrich, Frank; Gonzalez, Miguel A; Fragneto, Giovanna; Watkins, Erik; Ballone, Pietro

    2014-10-23

    Neutron reflectometry (NR) measurements were carried out to probe the structure and stability of two model biomembranes consisting of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) phospholipid bilayers hydrated by water solutions of two prototypical room-temperature ionic liquids (RTILs), namely, 1-butyl-3-methyl-imidazolium chloride ([bmim][Cl]) and choline chloride ([Chol][Cl]) at concentrations of 0.1 M and 0.5 M, respectively. The raw data were analyzed by fitting a distribution of scattering length densities arising from the different chemical species in the system. The results of this analysis show that (a) for all systems and concentrations that we considered, the thickness of the bilayers shrinks by ∼1 Å upon dissolving the ionic liquid into water and that (b) the RTIL ions enter the bilayer, finding their way to a preferred location in the lipid range that is nearly independent of the lipid and of the [bimim](+) or [Chol](+) choice. The volume fraction of RTIL sorbed in/on the bilayer, however, does depend on the lipid, but, again, is the same for [bmim][Cl] and for [Chol][Cl]. Thus, the RTIL occupies ∼5% of the bilayer volume in POPC, rising to ∼10% in DMPC. Repeating the measurements and data analysis after rinsing in pure water shows that the changes in the bilayer due to the RTIL sorption are irreversible and that a measurable amount of IL remains in the lipid fraction, that is, ∼2.5% of the bilayer volume in POPC and ∼8% in DMPC. PMID:25251987

  10. Electrochemical detection of arsenic(III) completely free from noble metal: Fe3O4 microspheres-room temperature ionic liquid composite showing better performance than gold.

    PubMed

    Gao, Chao; Yu, Xin-Yao; Xiong, Shi-Quan; Liu, Jin-Huai; Huang, Xing-Jiu

    2013-03-01

    In recent decades, electrochemical detection of arsenic(III) has been undergoing revolutionary developments with higher sensitivity and lower detection limit. Despite great success, electrochemical detection of As(III) still depends heavily on noble metals (predominantly Au) in a strong acid condition, thus increasing the cost and hampering the widespread application. Here, we report a disposable platform completely free from noble metals for electrochemical detection of As(III) in drinking water under nearly neutral condition by square wave anodic stripping voltammetry. By combining the high adsorptivity of Fe3O4 microspheres toward As(III) and the advantages of room temperature ionic liquid (RTIL), the Fe3O4-RTIL composite modified screen-printed carbon electrode (SPCE) showed even better electrochemical performance than commonly used noble metals. Several ionic liquids with different viscosities and surface tensions were found to have a different effect on the voltammetric behavior toward As(III). Under the optimized conditions, the Fe3O4-RTIL composites offered direct detection of As(III) within the desirable range (10 ppb) in drinking water as specified by the World Health Organization (WHO), with a detection limit (3σ method) of 8 × 10(-4) ppb. The obtained sensitivity was 4.91 μA ppb(-1), which is the highest as far as we know. In addition, a possible mechanism for As(III) preconcentration based on adsorption has been proposed and supported by designed experiments. Finally, this platform was successfully applied to analyzing a real sample collected from Inner Mongolia, China. PMID:23374085

  11. Template-free electrodeposition of AlFe alloy nanowires from a room-temperature ionic liquid as an anode material for Li-ion batteries.

    PubMed

    Chen, Gang; Chen, Yuqi; Guo, Qingjun; Wang, Heng; Li, Bing

    2016-08-15

    AlFe alloy nanowires were directly electrodeposited on copper substrates from trimethylamine hydrochloride (TMHC)-AlCl3 ionic liquids with small amounts of FeCl3 at room temperature without templates. Coin cells composed of AlFe alloy nanowire electrodes and lithium foils were assembled to characterize the alloy electrochemical properties by galvanostatic charge/discharge tests. Effects of FeCl3 concentration, potential and temperature on the alloy morphology, composition and cyclic performance were examined. Addition of Fe into the alloy changed the nanowires from a 'hill-like' bulk morphology to a free-standing morphology, and increased the coverage area of the alloy on Cu substrates. As an inactive element, Fe could also buffer the alloys' large volume changes during Li intercalation and deintercalation. AlFe alloy nanowires composed of a small amount of Fe with an average diameter of 140 nm exhibited an outstanding cyclic performance and delivered a specific capacity of about 570 mA h g(-1) after 50 cycles. This advanced template-free method for the direct preparation of high performance nanostructure AlFe alloy anode materials is quite simple and inexpensive, which presents a promising prospect for practical application in Li-ion batteries. PMID:27200436

  12. An electrochemical biosensor for alpha-fetoprotein based on carbon paste electrode constructed of room temperature ionic liquid and gold nanoparticles.

    PubMed

    Ding, Caifeng; Zhao, Fei; Ren, Rui; Lin, Jin-Ming

    2009-05-15

    A novel and effective electrochemical immunosensor for the rapid determination of alpha-fetoprotein (AFP) based on carbon paste electrode (CPE) consisting of room temperature ionic liquid (RTIL) N-butylpyridinium hexafluorophosphate (BPPF(6)) and graphite. The surface of the CPE was modified with gold nanoparticles for the immobilization of the alpha-fetoprotein antibody (anti-AFP). By sandwiching the antigen between anti-AFP on the CPE modified with gold nanoparticles and the secondary antibody, polyclonal anti-human-AFP labeled with horseradish peroxidase (HRP-labeled anti-AFP), the immunoassay was established. The concentration of AFP was determined based on differential pulse voltammetry (DPV) signal, which was generated in the reaction between O-aminophenol (OAP) and H(2)O(2) catalyzed by HRP labeled on the sandwich immunosensor. AFP concentration could be measured in a linear range of 0.50-80.00 ng mL(-1) with a detection limit of 0.25 ng mL(-1). The immunosensor exhibited high sensitivity and good stability, and would be valuable for clinical assay of AFP. PMID:19269485

  13. Study of the effect of tribo-materials and surface finish on the lubricant performance of new halogen-free room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Saurín, N.; Minami, I.; Sanes, J.; Bermúdez, M. D.

    2016-03-01

    The present work evaluates different materials and surface finish in the presence of newly designed, hydrophobic halogen-free room temperature ionic liquids (RTILs) as lubricants. A reciprocating tribo-tester was employed with steel-ceramic and steel-thermosetting epoxy resin contacts under boundary lubrication conditions. Four different tetraalkylphosphonium organosilanesulfonate RTILs provided excellent lubricating performance, with friction coefficients as low as 0.057, and non-measurable wear for the higher roughness machine-finish stainless steel flat against sapphire balls, in the case of the lubricants containing the 2-trimethylsilylethanesulfonate anion. Higher friction coefficients of the order of 0.1 and wear volumes of the order of 10-4 mm3 were observed for the lower roughness fine-finished flat stainless steel surface. All RTILs prevent wear of epoxy resin against stainless steel balls, with friction coefficients in the range of 0.03-0.06. EDX analysis shows the presence of RTILs on the stainless steel surfaces after the tribological tests. Under the experimental conditions, no corrosive processes were observed.

  14. Study of the translational diffusion of the benzophenone ketyl radical in comparison with stable molecules in room temperature ionic liquids by transient grating spectroscopy

    SciTech Connect

    Nishiyama, Y.; Fukuda, M.; Terazima, M.; Kimura, Y.

    2008-04-28

    Transient grating (TG) spectroscopy has been applied to the photoinduced hydrogen-abstraction reaction of benzophenone (BP) in various kinds of room temperature ionic liquids (RTILs). After the photoexcitation of BP in RTILs, the formation of a benzophenone ketyl radical (BPK) was confirmed by the transient absorption method, and the TG signal was analyzed to determine the diffusion coefficients of BPK and BP. For comparison, diffusion coefficients of carbon monoxide (CO), diphenylacetylene (DPA), and diphenylcyclopropenone (DPCP) in various RTILs were determined by the TG method using the photodissociation reaction of DPCP. While the diffusion coefficients of the stable molecules BP, DPA, and DPCP were always larger than those predicted by the Stokes-Einstein (SE) relation in RTILs, that of BPK was much smaller than those of the stable molecules and relatively close to that predicted by the SE relation in all solvents. For the smallest molecule CO, the deviation from the SE relation was evident. The diffusion coefficients of stable molecules are better represented by a power law of the inverse of the viscosity when the exponent was less than unity. The ratios of the diffusion coefficient of BP to that of BPK were larger in RTILs (2.7-4.0) than those (1.4-2.3) in conventional organic solvents. The slow diffusion of BPK in RTILs was discussed in terms of the fluctuation of the local electric field produced by the surrounding solvent ions.

  15. Physically Gelled Room-Temperature Ionic Liquid-Based Composite Membranes for CO2/N-2 Separation: Effect of Composition and Thickness on Membrane Properties and Performance

    SciTech Connect

    Nguyen, PT; Voss, BA; Wiesenauer, EF; Gin, DL; Nobe, RD

    2013-07-03

    An aspartame-based, low molecular-weight organic gelator (LMOG) was used to form melt-infused and composite membranes with two different imidazolium-based room-temperature ionic liquids (RTILs) for CO2 separation from N-2. Previous work demonstrated that LMOGs can gel RTILs at low, loading levels, and this aspartame-based LMOG was selected because it has been reported to gel a large number of RTILs. The imidazolium-based RTILs were used because of their inherent good properties for CO2/light gas separations. Analysis of the resulting bulk RTIL/LMOG physical gels showed that these materials have high sol-gel transition temperatures (ca. 135 degrees C) suitable for flue gas applications. Gas permeabilities and burst pressure measurements of thick, melt infused membranes revealed a trade-off between high CO2 permeabilities and good mechanical stability as a function of the LMOG loading. Defect-free, composite membranes of the gelled RTILs were successfully fabricated by choosing an appropriate porous membrane support (hydrophobic PTFE) using a suitable coating technique (roller coating). The thicknesses of the applied composite gel layers ranged from 10.3 to 20.7 mu m, which represents an order of magnitude decrease in active layer thickness, compared to the original melt-infused gel RTIL membranes.

  16. Theinfluence of a hierarchical porous carbon network on the coherent dynamics of a nanoconfined room temperature ionic liquid: A neutron spin echo and atomistic simulation investigation

    SciTech Connect

    Banuelos, Jose Leo; Feng, Guang; Fulvio, Pasquale F; Li, Song; Rother, Gernot; Arend, Nikolas; Faraone, Antonio; Dai, Sheng; Cummings, Peter T; Wesolowski, David J

    2014-01-01

    The molecular-scale dynamic properties of the room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, or [C4mim+ ][Tf2N ], confined in hierarchical microporous mesoporous carbon, were investigated using neutron spin echo (NSE) and molecular dynamics (MD) simulations. Both NSE and MD reveal pronounced slowing of the overall collective dynamics, including the presence of an immobilized fraction of RTIL at the pore wall, on the time scales of these approaches. A fraction of the dynamics, corresponding to RTIL inside 0.75 nm micropores located along the mesopore surfaces, are faster than those of RTIL in direct contact with the walls of 5.8 nm and 7.8 nm cylindrical mesopores. This behavior is ascribed to the near-surface confined-ion density fluctuations resulting from the ion ion and ion wall interactions between the micropores and mesopores as well as their confinement geometries. Strong micropore RTIL interactions result in less-coordinated RTIL within the micropores than in the bulk fluid. Increasing temperature from 296 K to 353 K reduces the immobilized RTIL fraction and results in nearly an order of magnitude increase in the RTIL dynamics. The observed interfacial phenomena underscore the importance of tailoring the surface properties of porous carbons to achieve desirable electrolyte dynamic behavior, since this impacts the performance in applications such as electrical energy storage devices.

  17. Ultrafast transient absorption spectrum of the room temperature Ionic liquid 1-hexyl-3-methylimidazolium bromide: Confounding effects of photo-degradation

    NASA Astrophysics Data System (ADS)

    Musat, Raluca M.; Crowell, Robert A.; Polyanskiy, Dmitriy E.; Thomas, Marie F.; Wishart, James F.; Katsumura, Yosuke; Takahashi, Kenji

    2015-12-01

    The photochemistry of the charge transfer (CT) band of the room temperature ionic liquid (RTIL) 1-hexyl-3-methylimidazolium bromide (HMIm+/Br-) is investigated using near-IR to vis ultrafast transient absorption (TA) and steady-state UV absorption spectroscopies. Continuous irradiation of the CT band at 266 nm results in the formation of photo-products that absorb strongly at 266 nm. It is shown that these photo-products, which are apparently very stable, adversely affect ultrafast TA measurements. Elimination of these effects reveals at least two transient species that exist within the TA detection window of 100 fs to 3 ns and 500-1250 nm. One of the components is a short-lived (<1 ps) species that absorbs at 1080 nm. The second band exhibits a multicomponent spectrum that is very broad with an absorption maximum around 600 nm and a lifetime that is longer than the 3 ns window of our TA spectrometer. Within the signal to noise ratio of the TA spectrometer little to no solvated electron is generated by the CT mechanism.

  18. Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

    SciTech Connect

    Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; Meisner, Roberta Ann; Meyer, III, Harry M.; Luo, Huimin; Delmau, Laetitia Helene; Dai, Sheng; Moyer, Bruce A

    2013-11-11

    Our study demonstrates a direct electrodeposition of UO2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO2(NTf2)2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM+NTf2). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. The UO2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).

  19. Determination of solute partition behavior with room-temperature ionic liquid based micellar gas-liquid chromatography stationary phases using the pseudophase model.

    PubMed

    Lantz, Andrew W; Pino, Verónica; Anderson, Jared L; Armstrong, Daniel W

    2006-05-19

    The use of micelles in ionic liquid based gas-chromatography stationary phases was evaluated using equations derived for a "three-phase" model. This model allows the determination of all three partition coefficients involved in the system, and elucidates the micellar contribution to retention and selectivity. Four types of micellar-ionic liquid columns were examined in this study: 1-butyl-3-methylimidazolium chloride with sodium dodecylsulfate or dioctyl sulfosuccinate, and 1-butyl-3-methylimidazolium hexafluorophosphate with polyoxyethylene-100-stearyl ether or polyoxyethylene-23-lauryl ether. The partition coefficients were measured for a wide range of probe molecules capable of a variety of types and magnitudes of interactions. In general, most probe molecules preferentially partitioned to the micellar pseudophase over the bulk ionic liquid component of the stationary phase. Therefore, addition of surfactant to the stationary phase usually resulted in greater solute retention. It is also shown that the selectivity of the stationary phase is significantly altered by the presence of micelles, either by enhancing or lessening the separation. The effects of surfactant on the interaction parameters of the stationary phase are determined using the Abraham solvation parameter model. The addition of sodium dodecylsulfate and dioctyl sulfosuccinate to 1-butyl-3-methylimidazolium chloride stationary phases generally increased the phase's hydrogen bond basicity and increased the level of dispersion interaction. Polyoxyethylene-100-stearyl ether and polyoxyethylene-23-lauryl ether surfactants, however, enhanced the pi-pi/n-pi, polarizability/dipolarity, and hydrogen bond basicity interactions of 1-butyl-3-methylimidazolium hexafluorophosphate to a greater degree than the ionic surfactants with 1-butyl-3-methylimidazolium chloride. However, these nonionic surfactants appeared to hinder the ability of the stationary phase to interact with solutes via dispersion forces

  20. 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.

    PubMed

    Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

    2016-06-30

    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. PMID:27243107

  1. Room temperature ionic liquid-based dispersive liquid phase microextraction for the separation/preconcentration of trace Cd(2+) as 1-(2-pyridylazo)-2-naphthol (PAN) complex from environmental and biological samples and determined by FAAS.

    PubMed

    Khan, Sumaira; Soylak, Mustafa; Kazi, Tasneem Gul

    2013-12-01

    The current work develops a new green methodology for the separation/preconcentration of cadmium ions (Cd(2+)) using room temperature ionic liquid-dispersive liquid phase microextraction (RTIL-DLME) prior to analysis by flame atomic absorption spectrometry with microsample introduction system. Room temperature ionic liquids (RTIL) are considered "Green Solvents" for their thermally stable and non-volatile properties, here 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] was used as an extractant. The preconcentration of Cd(2+) in different waters and acid digested scalp hair samples were complexed with 1-(2-pyridylazo)-2-naphthol and extracted into the fine drops of RTILs. Some significant factors influencing the extraction efficiency of Cd(2+) and its subsequent determination, including pH, amount of ligand, volume of RTIL, dispersant solvent, sample volume, temperature, and incubation time were investigated in detail. The limit of detection and the enhancement factor under the optimal conditions were 0.05 μg/L and 50, respectively. The relative standard deviation of 100 μg/L Cd(2+) was 4.3 %. The validity of the proposed method was checked by determining Cd(2+) in certified reference material (TM-25.3 fortified water). The sufficient recovery (>98 %) of Cd(2+) with the certified value. The mean concentrations of Cd in lake water 13.2, waste water 15.7 and hair sample 16.8 μg/L, respectively and the developed method was applied satisfactorily to the preconcentration and determination of Cd(2+) in real samples. PMID:24197606

  2. States and migration of an excess electron in a pyridinium-based, room-temperature ionic liquid: an ab initio molecular dynamics simulation exploration.

    PubMed

    Wang, Zhiping; Zhang, Liang; Cukier, Robert I; Bu, Yuxiang

    2010-02-28

    The structural and electronic properties of an excess electron (EE) in the ionic liquid (IL) 1-methylpyridinium chloride were explored using ab initio molecular dynamics simulations and quantum chemical calculations to give an overall understanding of the solvation and transport behavior of an EE in this IL. The results show that the EE resides in cation pi*-type orbitals and that the electronic states can be characterized by the alternating appearance of localized and delocalized states during the time evolution. The characters of the EE electronic states are determined by the number of cations contributing to the LUMO of the IL. In a localized state one or two cations contribute to the LUMO of the bulk ionic liquid, while in the delocalized state the IL LUMO is composed of pi*-type orbitals spanning nearly all the cations in the cell. The arrangement and fluctuation-induced changes of the orbital components in the empty band produce an alternation of different states and leads to the migration of the excess electron. These findings can be attributed to the special features of the electronic structures and geometries of the IL, and they can be used to explain similarities and differences between pyridinium-based and imidazolium-based ILs in mediating electron migration. PMID:20145852

  3. Heterogeneous Nature of Relaxation Dynamics of Room-Temperature Ionic Liquids (EMIm)2[Co(NCS)4] and (BMIm)2[Co(NCS)4

    DOE PAGESBeta

    Hensel-Bielowka, Stella; Wojnarowska, Zaneta; Dzida, Marzena; Zorębski, Edward; Zorębski, Michał; Geppert-Rybczyńska, Monika; Peppel, Tim; Grzybowska, Katarzyna; Wang, Yangyang; Sokolov, Alexei P.; et al

    2015-08-11

    Dynamic crossover above Tg has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel–Fulcher–Tammann dependence or a breakdown of the Stokes–Einstein and related relations. In this study, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm)2[Co(NCS)4] and (EMIm)2[Co(NCS)4] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observed in the entire studied temperature range. On themore » contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Finally and moreover, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole–Cole function should be used instead.« less

  4. Effect of Room Temperature Ionic Liquid on the Formation of the Complex Oxalate-Sodium Morin-5-Sulfonate-Aluminium(III): Application to the Fluorescence Determination of Oxalate Ion.

    PubMed

    Nizar, Syaza Atikah; Mohd Suah, Faiz Bukhari

    2016-07-01

    The effect of room temperature ionic liquid (RTIL) on the formation of the fluorescence ternary complex oxalate-sodium morin-5-sulfonate (NaMSA)-Aluminium(III) has been studied. In weakly acidic medium and in the presence of RTIL, 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6), total complex formation is achieved as compared with the formation of the binary complex of NaMSA-Aluminium(III). The fluorescence characteristics of the system allowed the establishment of a very sensitive method for the spectrofluorimetric determination of oxalate ion. The ternary complex formed its highest fluorescence signal at 513 nm and excitation at 420 nm. In these conditions, the method produces a detection limit of 0.57 ng mL(-1). The procedure has been satisfactorily applied to the determination of oxalate ion in a vegetal tissue (spinach leaves). PMID:27286697

  5. Probing solute-solvent interaction in 1-ethyl-3-methylimidazolium-based room temperature ionic liquids: A time-resolved fluorescence anisotropy study.

    PubMed

    Das, Sudhir Kumar; Sarkar, Moloy

    2014-03-01

    Rotational diffusion of two organic solutes, coumarin153 (C153) and 4-aminophthalimide (AP) has been investigated in four ionic liquids (ILs), viz. 1-ethyl-3-methylimidazolium trifluoroacetate (EMIMTFA), 1-ethyl-3-methylimidazolium ethylsulfate (EMIMESU), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMTFB) and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIMTCB), as a function of temperature. Between the two probes, AP can act as hydrogen-bond-donor to the solvents having hydrogen bond acceptor ability. The results indicate that the rotational dynamics of C153 is mainly governed by the viscosity of the medium. On the other hand, the rotational motion of AP is found to be significantly hindered in the ILs depending on the nature of anions of the ILs. Rotational coupling constant values for AP in the ILs follow the order TFA > ESU > TCB > TFB. The slower rotational motion of AP in these ILs has been attributed to the specific hydrogen bonding interaction between AP and anions of ILs. PMID:24158315

  6. SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid.

    PubMed

    Hirosawa, Kazu; Fujii, Kenta; Ueki, Takeshi; Kitazawa, Yuzo; Littrell, Kenneth C; Watanabe, Masayoshi; Shibayama, Mitsuhiro

    2016-07-21

    We have utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d8-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d8-[C2mIm(+)][TFSA(-)]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at Tc. Furthermore, we evaluated the enthalpic and entropic contributions to the effective interaction parameter χeff of PPhEtMA in [C2mIm(+)][TFSA(-)] and compared them with those of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χeff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. It was found out that the strong dependence of Tc on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χeff. PMID:27314165

  7. Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

    PubMed

    Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan

    2016-04-14

    Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies. PMID:26982480

  8. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin

    2011-11-01

    Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic ligand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

  9. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

    2008-09-09

    Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic liqand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

  10. Surface exploration of a room-temperature ionic liquid-chitin composite film decorated with electrochemically deposited PdFeNi trimetallic alloy nanoparticles by pattern recognition: an elegant approach to developing a novel biotin biosensor.

    PubMed

    Gholivand, Mohammad-Bagher; Jalalvand, Ali R; Goicoechea, Hector C; Paimard, Giti; Skov, Thomas

    2015-01-01

    In this study, a novel biosensing system for the determination of biotin (BTN) based on electrodeposition of palladium-iron-nickel (PdFeNi) trimetallic alloy nanoparticles (NPs) onto a glassy carbon electrode (GCE) modified with a room-temperature ionic liquid (RTIL)-chitin (Ch) composite film (PdFeNi/ChRTIL/GCE) is established. NPs have a wide range of applications in science and technology and their sizes are often measured using transmission electron microscopy (TEM) or X-ray diffraction. Here, we used a pattern recognition method (digital image processing, DIP) for measuring particle size distributions (PSDs) from scanning electron microscopic (SEM) images in the presence of an uneven background. Different depositions were performed by varying the number of cyclic potential scans (N) during electroreduction step. It was observed that the physicochemical properties of the deposits were correlated to the performance of the PdFeNi/ChRTIL/GCE with respect to BTN assay. The best results were obtained for eight electrodeposition cyclic scans, where small-sized particles (19.54 ± 6.27 nm) with high density (682 particles µm(-2)) were obtained. Under optimized conditions, a linear range from 2.0 to 44.0 × 10(-9) mol L(-1) and a limit of detection (LOD) of 0.6 × 10(-9) mol L(-1) were obtained. The PdFeNi/ChRTIL nanocomposite showed excellent compatibility, enhanced electron transfer kinetics, large electroactive surface area, and was highly sensitive, selective, and stable toward BTN determination. Finally, the PdFeNi/ChRTIL/GCE was satisfactorily applied to the determination of BTN in infant milk powder, liver, and egg yolk samples. PMID:25281100

  11. New insight of coordination and extraction of uranium(VI) with N-donating ligands in room temperature ionic liquids: N,N'-diethyl-N,N'-ditolyldipicolinamide as a case study.

    PubMed

    Yuan, Li-Yong; Sun, Man; Mei, Lei; Wang, Lin; Zheng, Li-Rong; Gao, Zeng-Qiang; Zhang, Jing; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-02-16

    Room temperature ionic liquids (RTILs) represent a recent new class of solvents applied in liquid/liquid extraction based nuclear fuel reprocessing, whereas the related coordination chemistry and detailed extraction processes are still not well understood and remain of deep fundamental interest. The work herein provides a new insight of coordination and extraction of uranium(VI) with N-donating ligands, e.g., N,N'-diethyl-N,N'-ditolyldipicolinamide (EtpTDPA), in commonly used RTILs. Exploration of the extraction mechanism, speciation analyses of the extracted U(VI), and crystallographic studies of the interactions of EtpTDPA with U(VI) were performed, including the first structurally characterized UO2(EtpTDPA)2(NTf2) and UO2(EtpTDPA)2(PF6)2 compounds and a first case of crystallographic differentiation between the extracted U(VI) complexes in RTILs and in molecular solvents. It was found that in RTILs two EtpTDPA molecules coordinate with one U(VI) ion through the carbonyl and pyridine nitrogen moieties, while NTf2(-) and PF6(-) act as counterions. The absence of NO3(-) in the complexes is coincident with a cation-exchange extraction. In contrast, both the extracted species and extraction mechanisms are greatly different in dichloromethane, in which UO2(2+) coordinates in a neutral complex form with one EtpTDPA molecule and two NO3(-) cations. In addition, the complex formation in RTILs is independent of the cation exchange since incorporating UO2(NO3)2, EtpTDPA, and LiNTf2 or KPF6 in a solution also produces the same complex as that in RTILs, revealing the important roles of weakly coordinating anions on the coordination chemistry between U(VI) and EtpTDPA. These findings suggest that cation-exchange extraction mode for ILs-based extraction system probably originates from the supply of weakly coordinating anions from RTILs. Thus the coordination of uranium(VI) with extractants as well as the cation-exchange extraction mode may be potentially changed by varying the

  12. Biocatalytic transformations in ionic liquids.

    PubMed

    van Rantwijk, Fred; Madeira Lau, Rute; Sheldon, Roger A

    2003-03-01

    Room temperature ionic liquids are non-volatile, thermally stable and highly polar; they are also moderately hydrophilic solvents. Here, we discuss their use as reaction media for biocatalysis. Enzymes of widely diverging types are catalytically active in ionic liquids or aqueous biphasic ionic liquid systems. Lipases, in particular, maintain their activity in anhydrous ionic liquid media; the (enantio)selectivity and operational stability are often better than in traditional media. The unconventional solvent properties of ionic liquids have been exploited in biocatalyst recycling and product recovery schemes that are not feasible with traditional solvent systems. PMID:12628370

  13. Room-temperature silver-containing liquid metal salts with nitrate anions.

    PubMed

    Schaltin, Stijn; Brooks, Neil R; Sniekers, Jeroen; Depuydt, Daphne; Van Meervelt, Luc; Binnemans, Koen; Fransaer, Jan

    2013-11-21

    The synthesis, structural, thermal and electrochemical properties of fluorine-free silver-containing ionic liquids are presented. The ionic liquid cations are formed by a silver(i) ion surrounded by two 1-alkylimidazole ligands, with the counter anions being nitrate ions. Depending on the alkyl chain length, the complexes were found to be liquids at room temperature or melting slightly above this. For the solid compounds it was possible to elucidate the structure by single crystal X-ray analysis. The ionic liquids are electroactive, have good mass transport properties and can be used for the electrodeposition of silver at high current densities. The thermal properties and stability of these compounds were tested by differential scanning calorimetry and thermogravimetric analysis. The viscosity of the ionic liquids follows a Vogel-Tamman-Fulcher relationship as a function of temperature. The electrochemical properties of the complexes were tested by cyclic voltammetry and the resulting electrodeposits were examined using scanning electron microscopy and atomic force microscopy. PMID:24097139

  14. 3-Methylpiperidinium ionic liquids.

    PubMed

    Belhocine, Tayeb; Forsyth, Stewart A; Gunaratne, H Q Nimal; Nieuwenhuyzen, Mark; Nockemann, Peter; Puga, Alberto V; Seddon, Kenneth R; Srinivasan, Geetha; Whiston, Keith

    2015-04-28

    A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEK® A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rmβpip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmmβpip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmmβpip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmmβpip]X (X(-) = I(-), [CF3CO2](-) or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 °C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)-1-methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended. PMID:25669485

  15. Phosphonium-based ionic liquids and uses

    SciTech Connect

    Del Sesto, Rico E; Koppisch, Andrew T; Lovejoy, Katherine S; Purdy, Geraldine M

    2014-12-30

    Phosphonium-based room temperature ionic liquids ("RTILs") were prepared. They were used as matrices for Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry and also for preparing samples of dyes for analysis.

  16. Multiwalled carbon nanotubes sensor for organic liquid detection at room temperature

    NASA Astrophysics Data System (ADS)

    Chaudhary, Deepti; Khare, Neeraj; Vankar, V. D.

    2016-04-01

    We have explored the possibility of using multiwalled carbon nanotubes (MWCNTs) as room temperature chemical sensor for the detection of organic liquids such as ethanol, propanol, methanol and toluene. MWCNTs were synthesized by thermal chemical vapor deposition (TCVD) technique. The interdigitated electrodes were fabricated by conventional photolithography technique. The sensor was fabricated by drop depositing MWCNT suspension onto the interdigitated electrodes. The sensing properties of MWCNTs sensor was studied for organic liquids detection. The resistance of sensor was found to increase upon exposure to these liquids. Sensor shows good reversibility and fast response at room temperature. Charge transfer between the organic liquid and sensing element is the dominant sensing mechanism.

  17. Room temperature supramolecular columnar liquid crystals formed by hydrogen bonding of isoquinoline derivatives

    NASA Astrophysics Data System (ADS)

    Hyup Lee, Jun; Lee, Seung Jun; Jho, Jae Young

    2014-07-01

    We report new self-assembled discotic liquid crystals exhibiting columnar mesophases at room temperature, which are constructed by intermolecular hydrogen bonding between the core of 1,3,5-trihydroxybenzene or 1,3,5-cyclohexanetricarboxylic acid and the peripheral molecules of isoquinoline derivatives. The mesomorphic properties of supramolecular liquid crystals were investigated by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction studies. The self-assembled liquid crystals exhibited rectangular columnar phases (Colro) with an ordered stacking structure of the mesogens in a column at room temperature, regardless of the type of the core molecule, due probably to the close-packed aromatic rings around a core molecule and the angular structure in three arms of the discotic mesogen. These room temperature columnar phases are rare examples for the discotic liquid crystals, and our findings in the present study provide a new way to prepare low melting columnar liquid crystalline materials for molecular electronics.

  18. Heterogeneous Nature of Relaxation Dynamics of Room-Temperature Ionic Liquids (EMIm)2[Co(NCS)4] and (BMIm)2[Co(NCS)4

    SciTech Connect

    Hensel-Bielowka, Stella; Wojnarowska, Zaneta; Dzida, Marzena; Zorębski, Edward; Zorębski, Michał; Geppert-Rybczyńska, Monika; Peppel, Tim; Grzybowska, Katarzyna; Wang, Yangyang; Sokolov, Alexei P.; Paluch, Marian

    2015-08-11

    Dynamic crossover above Tg has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel–Fulcher–Tammann dependence or a breakdown of the Stokes–Einstein and related relations. In this study, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm)2[Co(NCS)4] and (EMIm)2[Co(NCS)4] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observed in the entire studied temperature range. On the contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Finally and moreover, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole–Cole function should be used instead.

  19. Ionic liquids as novel solvents for ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew D.; Leo, Donald J.

    2004-07-01

    The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

  20. Migration of bisphenol A from can coatings to liquid infant formula during storage at room temperature.

    PubMed

    Cao, Xu-Liang; Corriveau, Jeannette; Popovic, Svetlana

    2009-12-01

    Information on migration of bisphenol A (BPA) from can coatings to foods during storage at room temperature is very limited, and the conclusions from the available studies are not always consistent. To investigate the effect of storage time on BPA migration from can coatings to liquid infant formula at room temperature, samples of 21 canned liquid infant formula products from different cans but the same lot as those analyzed for BPA previously were analyzed for BPA again after storage at room temperature for 10 months. Additional migration of BPA from can coatings to liquid formula during the 10-month storage period at room temperature was observed for 9 of the 21 products, with increases in BPA levels ranging from 29.8 to 110%. Significant differences between the 2007 and 2008 results (P = 0.026) were observed for only one brand of product, which had the lowest BPA levels in the 2007 survey. The BPA levels in the milk-based formula products analyzed in 2008 (mean, 6.8 ng/g) were significantly higher (P = 0.00023) than those in the milk-based formula products analyzed in 2007 (mean, 5.0 ng/g), whereas the differences in BPA levels between the soya-based formula products analyzed in 2008 (mean, 5.3 ng/g) and those analyzed in 2007 (mean, 5.8 ng/g) were not significant (P = 0.097). No obvious correlation between the product expiration date and the level of BPA migration from can coatings was observed. PMID:20003741

  1. Ionic Liquids Database- (ILThermo)

    National Institute of Standards and Technology Data Gateway

    SRD 147 Ionic Liquids Database- (ILThermo) (Web, free access)   IUPAC Ionic Liquids Database, ILThermo, is a free web research tool that allows users worldwide to access an up-to-date data collection from the publications on experimental investigations of thermodynamic, and transport properties of ionic liquids as well as binary and ternary mixtures containing ionic liquids.

  2. Externally Wetted Ionic Liquid Thruster

    NASA Astrophysics Data System (ADS)

    Lozano, P.; Martinez-Sanchez, M.; Lopez-Urdiales, J. M.

    2004-10-01

    This paper presents initial developments of an electric propulsion system based on ionic liquid ion sources (ILIS). Propellants are ionic liquids, which are organic salts with two important characteristics; they remain in the liquid state at room temperature and have negligible vapor pressure, thus allowing their use in vacuum. The working principles of ILIS are similar to those of liquid metal ion sources (LMIS), in which a Taylor cone is electrostatically formed at the tip of an externally wetted needle while ions are emitted directly from its apex. ILIS have the advantage of being able to produce negative ions that have similar masses than their positive counterparts with similar current levels. This opens up the possibility of achieving plume electrical neutrality without electron emitters. The possible multiplexing of these emitters is discussed in terms of achievable thrust density for applications other than micro-propulsion.

  3. Room-temperature ionic liquids: a novel versatile lubricant.

    PubMed

    Ye, C; Liu, W; Chen, Y; Yu, L

    2001-11-01

    Alkylimidazolium tetrafluoroborates are promising versatile lubricants for the contact of steel/steel, steel/aluminium, steel/copper, steel/SiO2, Si3N4/SiO2, steel/Si(100), steel/sialon ceramics and Si3N4/sialon ceramics; they show excellent friction reduction, antiwear performance and high load-carrying capacity. PMID:12240132

  4. Room Temperature Bubble Point Tests on Porous Screens: Implications for Cryogenic Liquid Acquisition Devices

    NASA Technical Reports Server (NTRS)

    Hartwig, Jason; Mann, J. Adin, Jr.

    2012-01-01

    We present experimental results for room temperature bubble point tests conducted at the Cedar Creek Road Cryogenic Complex, Cell 7 (CCL-7) at the NASA Glenn Research Center. The purpose of these tests was to investigate the performance of three different fine mesh screens in room temperature liquids to provide pretest predictions in cryogenic liquid nitrogen (LN2) and hydrogen (LH2) as part of NASA's microgravity LAD technology development program. Bench type tests based on the maximum bubble point method were conducted for a 325 x 2300, 450 x 2750, and 510 x 3600 mesh sample in pure room temperature liquid methanol, acetone, isopropyl alcohol, water, and mixtures of methanol and water to cover the intermediate to upper surface tension range. A theoretical model for the bubble point pressure is derived from the Young-LaPlace equation for the pressure drop across a curved interface. Governing equations are reduced in complexity through a set of simplifying assumptions to permit direct comparison with the experimental data. Screen pore sizes are estimated from scanning electron microscopy (SEM) to make pretest predictions. Pore sizes based on SEM analysis are compared with historical data available in the literature for the 325 x 2300 and 450 x 2750 screens as well with data obtained from bubble point tests conducted in this work. Experimental results show that bubble point pressure is proportional to the surface tension of the liquid. We show that there is excellent agreement between data and model for pure fluids when the data is corrected for non-zero contact angle measured on the screens using a modified Sessile Drop technique. SEM image analysis of the three meshes indicated that bubble point pressure would be a maximum for the finest mesh screen. The pore diameters based on SEM analysis and experimental data obtained here are in excellent agreement for the 325 x 2300 and 450 x 2750 meshes, but not for the finest 510 x 3600 mesh. Therefore the simplified model

  5. Measurement of the Order Parameter in a Room Temperature Liquid Crystal: An Experiment for the Physical Chemistry Laboratory.

    ERIC Educational Resources Information Center

    DuPre, Donald B.; Chapoy, L. Lawrence

    1979-01-01

    Presented here is a laboratory experiment for a course in physical chemistry. Students are requested to directly measure the degree of orientational order in a liquid crystal at room temperature. A minimum amount of equipment is necessary. (Author/SA)

  6. Ab initio spur size calculation in liquid water at room temperature

    NASA Astrophysics Data System (ADS)

    Muroya, Yusa; Mozumder, Asokendu

    2016-07-01

    An attempt was made to calculate the spur size in liquid water at room temperature from fundamental interactions. Electron trapping, elastic scattering, and positive-ion back attraction undergone in sub-excitation and sub-vibrational stages in the 100 fs time scale for thermalization were considered and included in the model. Overall diffusional broadening was estimated to be 41.2 Å, attended by the positive-ion pull back of 24.0 Å, resulting in a calculated spur size of 17.2 Å. Electron trapping is seen in competition with thermalization in the ultimate stage, which results in the trapped electron position distribution as a sum of Gaussians.

  7. Ionic Liquids to Replace Hydrazine

    NASA Technical Reports Server (NTRS)

    Koelfgen, Syri; Sims, Joe; Forton, Melissa; Allan, Barry; Rogers, Robin; Shamshina, Julia

    2011-01-01

    A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

  8. Acidic Ionic Liquids.

    PubMed

    Amarasekara, Ananda S

    2016-05-25

    Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition. PMID:27175515

  9. Effects of Ionic Dependence of DNA Persistence Length on the DNA Condensation at Room Temperature

    NASA Astrophysics Data System (ADS)

    Mao, Wei; Liu, Yan-Hui; Hu, Lin; Xu, Hou-Qiang

    2016-05-01

    DNA persistence length is a key parameter for quantitative interpretation of the conformational properties of DNA and related to the bending rigidity of DNA. A series of experiments pointed out that, in the DNA condensation process by multivalent cations, the condensed DNA takes elongated coil or compact globule states and the population of the compact globule states increases with an increase in ionic concentration. At the same time, single molecule experiments carried out in solution with multivalent cations (such as spermidine, spermine) indicated that DNA persistence length strongly depends on the ionic concentration. In order to revolve the effects of ionic concentration dependence of persistence length on DNA condensation, a model including the ionic concentration dependence of persistence length and strong correlation of multivalent cation on DNA is provided. The autocorrelation function of the tangent vectors is found as an effective way to detect the ionic concentration dependence of toroidal conformations. With an increase in ion concentration, the first periodic oscillation contained in the autocorrelation function shifts, the number of segment contained in the first periodic oscillation decreases gradually. According to the experiments, the average long-axis length is defined to estimate the ionic concentration dependence of condensation process further. The relation between long-axis length and ionic concentration matches the experimental results qualitatively. Supported by National Natural Science Foundation of China under Grant Nos. 11047022, 11204045, 11464004 and 31360215; The Research Foundation from Ministry of Education of China (212152), Guizhou Provincial Tracking Key Program of Social Development (SY20123089, SZ20113069); The General Financial Grant from the China Postdoctoral Science Foundation (2014M562341); The Research Foundation for Young University Teachers from Guizhou University (201311); The West Light Foundation (2015) and College

  10. Thermodynamics and micro heterogeneity of ionic liquids.

    PubMed

    Gomes, Margarida F Costa; Lopes, J N Canongia; Padua, A A H

    2010-01-01

    The high degree of organisation in the fluid phase of room-temperature ionic liquids has major consequences on their macroscopic properties, namely on their behaviour as solvents. This nanoscale self-organisation is the result of an interplay between two types of interaction in the liquid phase - Coulomb and van der Waals - that eventually leads to the formation of medium-range structures and the recognition of some ionic liquids as composed of a high-charge density, cohesive network permeated by low-charge density regions.In this chapter, the structure of the ionic liquids will be explored and some of their consequences to the properties of ionic liquids analyzed. PMID:21107797

  11. Liquid Phase Chemical-Enhanced Oxidation for GaAs Operated Near Room Temperature

    NASA Astrophysics Data System (ADS)

    Wang, Hwei-Heng; Huang, Chien-Jung; Wang, Yeong-Her; Houng, Mau-Phon

    1998-01-01

    A new chemical enhanced oxidation method for gallium arsenide (GaAs) in liquid phase near room temperature (40°C 70°C) is proposed and investigated. Featureless oxide layers with good uniformity and reliability can be grown efficiently on GaAs without any extra energy source. A relatively high oxidation rate (≃1000 Å/h), about 50 times higher than that obtained during oxidation in boiling water has been realized. Based on the results of X-ray photoelectron spectroscopy (XPS), excellent chemical stability after thermal annealing as well as good chemical stoichiometry have been realized. The oxide was determined to be composed of Ga2O3 and As2O3.

  12. Use of ionic liquids as coordination ligands for organometallic catalysts

    DOEpatents

    Li, Zaiwei; Tang, Yongchun; Cheng; Jihong

    2009-11-10

    Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

  13. Direct Writing of Flexible Electronics through Room Temperature Liquid Metal Ink

    PubMed Central

    Gao, Yunxia; Li, Haiyan; Liu, Jing

    2012-01-01

    Background Conventional approaches of making a flexible circuit are generally complex, environment unfriendly, time and energy consuming, and thus expensive. Here, we describe for the first time the method of using high-performance GaIn10-based electrical ink, a significantly neglected room temperature liquid metal, as both electrical conductors and interconnects, for directly writing flexible electronics via a rather easy going and cost effective way. Methods The new generation electric ink was made and its wettability with various materials was modified to be easily written on a group of either soft or rigid substrates such as epoxy resin board, glass, plastic, silica gel, paper, cotton, textiles, cloth and fiber etc. Conceptual experiments were performed to demonstrate and evaluate the capability of directly writing the electrical circuits via the invented metal ink. Mechanisms involved were interpreted through a series of fundamental measurements. Results The electrical resistivity of the fluid like GaIn10-based material was measured as 34.5 µΩ·cm at 297 K by four point probe method and increased with addition of the oxygen quantity, which indicates it as an excellent metal ink. The conductive line can be written with features that are approximately 10 µm thick. Several functional devices such as a light emitting diode (LED) array showing designed lighting patterns and electrical fan were made to work by directly writing the liquid metal on the specific flexible substrates. And satisfactory performances were obtained. Conclusions The present method opens the way to directly and quickly writing flexible electronics which can be as simple as signing a name or drawing a picture on the paper. The unique merit of the GaIn10-based liquid metal ink lies in its low melting temperature, well controlled wettability, high electrical conductivity and good biocompability. The new electronics writing strategy and basic principle has generalized purpose and can be

  14. Formulation of a room temperature ferroelectric liquid crystal mixture with sub-millisecond switching time

    NASA Astrophysics Data System (ADS)

    Debnath, A.; Sinha, D.; Mandal, P. K.; Dabrowski, R.

    2015-06-01

    Ferroelectric liquid crystal (FLC) based display devices show faster response compared to nematic LC based devices. Since pure FLC compounds are high temperature LCs and do not possess optimum parameters necessary for display devices, a room temperature FLC mixture has been formulated, first time by any Indian group. The mixture is prepared by doping an appropriate chiral compound in a four-component LC based achiral host mixture. Resulting mixture was characterized using optical polarizing microscopy, frequency domain dielectric spectroscopy and electro-optic methods. It shows very wide range ferroelectric SmC* phase followed by paraelectric SmA* phase (Cr< 19°CSmC*89°C SmA* 108°C I) which would facilitate attaining book shelf geometry alignment in display devices. Dielectric spectroscopy study reveals Goldstone (in kHz region) and soft mode (in hundred kHz region) relaxations in SmC* and SmA* phases respectively. The mixture possesses moderate tilt angle (34.5° - 13°), low viscosity (0.9 - 0.05 N.s.m-2) and moderately high spontaneous polarization (112 - 36 nC.cm-2) which decrease with temperature. These result in very fast switching, slowest response time being 475 µs at ambient temperature.

  15. Room temperature ferromagnetism in liquid-phase pulsed laser ablation synthesized nanoparticles of nonmagnetic oxides

    NASA Astrophysics Data System (ADS)

    Singh, S. C.; Kotnala, R. K.; Gopal, R.

    2015-08-01

    Intrinsic Room Temperature Ferromagnetism (RTF) has been observed in undoped/uncapped zinc oxide and titanium dioxide spherical nanoparticles (NPs) obtained by a purely green approach of liquid phase pulsed laser ablation of corresponding metal targets in pure water. Saturation magnetization values observed for zinc oxide (average size, 9 ± 1.2 nm) and titanium dioxide (average size, 4.4 ± 0.3 nm) NPs are 62.37 and 42.17 memu/g, respectively, which are several orders of magnitude larger than those of previous reports. In contrast to the previous works, no postprocessing treatments or surface modification is required to induce ferromagnetism in the case of present communication. The most important result, related to the field of intrinsic ferromagnetism in nonmagnetic materials, is the observation of size dependent ferromagnetism. Degree of ferromagnetism in titanium dioxide increases with the increase in particle size, while it is reverse for zinc oxide. Surface and volume defects play significant roles for the origin of RTF in zinc oxide and titanium dioxide NPs, respectively. Single ionized oxygen and neutral zinc vacancies in zinc oxide and oxygen and neutral/ionized titanium vacancies in titanium dioxide are considered as predominant defect centres responsible for observed ferromagnetism. It is expected that origin of ferromagnetism is a consequence of exchange interactions between localized electron spin moments resulting from point defects.

  16. A room-temperature sodium rechargeable battery using an SO2-based nonflammable inorganic liquid catholyte

    PubMed Central

    Jeong, Goojin; Kim, Hansu; Sug Lee, Hyo; Han, Young-Kyu; Hwan Park, Jong; Hwan Jeon, Jae; Song, Juhye; Lee, Keonjoon; Yim, Taeeun; Jae Kim, Ki; Lee, Hyukjae; Kim, Young-Jun; Sohn, Hun-Joon

    2015-01-01

    Sodium rechargeable batteries can be excellent alternatives to replace lithium rechargeable ones because of the high abundance and low cost of sodium; however, there is a need to further improve the battery performance, cost-effectiveness, and safety for practical use. Here we demonstrate a new type of room-temperature and high-energy density sodium rechargeable battery using an SO2-based inorganic molten complex catholyte, which showed a discharge capacity of 153 mAh g−1 based on the mass of catholyte and carbon electrode with an operating voltage of 3 V, good rate capability and excellent cycle performance over 300 cycles. In particular, non-flammability and intrinsic self-regeneration mechanism of the inorganic liquid electrolyte presented here can accelerate the realization of commercialized Na rechargeable battery system with outstanding reliability. Given that high performance and unique properties of Na–SO2 rechargeable battery, it can be another promising candidate for next generation energy storage system. PMID:26243052

  17. Room temperature ferromagnetism in liquid-phase pulsed laser ablation synthesized nanoparticles of nonmagnetic oxides

    SciTech Connect

    Singh, S. C. Gopal, R.; Kotnala, R. K.

    2015-08-14

    Intrinsic Room Temperature Ferromagnetism (RTF) has been observed in undoped/uncapped zinc oxide and titanium dioxide spherical nanoparticles (NPs) obtained by a purely green approach of liquid phase pulsed laser ablation of corresponding metal targets in pure water. Saturation magnetization values observed for zinc oxide (average size, 9 ± 1.2 nm) and titanium dioxide (average size, 4.4 ± 0.3 nm) NPs are 62.37 and 42.17 memu/g, respectively, which are several orders of magnitude larger than those of previous reports. In contrast to the previous works, no postprocessing treatments or surface modification is required to induce ferromagnetism in the case of present communication. The most important result, related to the field of intrinsic ferromagnetism in nonmagnetic materials, is the observation of size dependent ferromagnetism. Degree of ferromagnetism in titanium dioxide increases with the increase in particle size, while it is reverse for zinc oxide. Surface and volume defects play significant roles for the origin of RTF in zinc oxide and titanium dioxide NPs, respectively. Single ionized oxygen and neutral zinc vacancies in zinc oxide and oxygen and neutral/ionized titanium vacancies in titanium dioxide are considered as predominant defect centres responsible for observed ferromagnetism. It is expected that origin of ferromagnetism is a consequence of exchange interactions between localized electron spin moments resulting from point defects.

  18. A room-temperature sodium rechargeable battery using an SO2-based nonflammable inorganic liquid catholyte.

    PubMed

    Jeong, Goojin; Kim, Hansu; Lee, Hyo Sug; Han, Young-Kyu; Park, Jong Hwan; Jeon, Jae Hwan; Song, Juhye; Lee, Keonjoon; Yim, Taeeun; Kim, Ki Jae; Lee, Hyukjae; Kim, Young-Jun; Sohn, Hun-Joon

    2015-01-01

    Sodium rechargeable batteries can be excellent alternatives to replace lithium rechargeable ones because of the high abundance and low cost of sodium; however, there is a need to further improve the battery performance, cost-effectiveness, and safety for practical use. Here we demonstrate a new type of room-temperature and high-energy density sodium rechargeable battery using an SO2-based inorganic molten complex catholyte, which showed a discharge capacity of 153 mAh g(-1) based on the mass of catholyte and carbon electrode with an operating voltage of 3 V, good rate capability and excellent cycle performance over 300 cycles. In particular, non-flammability and intrinsic self-regeneration mechanism of the inorganic liquid electrolyte presented here can accelerate the realization of commercialized Na rechargeable battery system with outstanding reliability. Given that high performance and unique properties of Na-SO2 rechargeable battery, it can be another promising candidate for next generation energy storage system. PMID:26243052

  19. A room-temperature sodium rechargeable battery using an SO2-based nonflammable inorganic liquid catholyte

    NASA Astrophysics Data System (ADS)

    Jeong, Goojin; Kim, Hansu; Sug Lee, Hyo; Han, Young-Kyu; Hwan Park, Jong; Hwan Jeon, Jae; Song, Juhye; Lee, Keonjoon; Yim, Taeeun; Jae Kim, Ki; Lee, Hyukjae; Kim, Young-Jun; Sohn, Hun-Joon

    2015-08-01

    Sodium rechargeable batteries can be excellent alternatives to replace lithium rechargeable ones because of the high abundance and low cost of sodium; however, there is a need to further improve the battery performance, cost-effectiveness, and safety for practical use. Here we demonstrate a new type of room-temperature and high-energy density sodium rechargeable battery using an SO2-based inorganic molten complex catholyte, which showed a discharge capacity of 153 mAh g-1 based on the mass of catholyte and carbon electrode with an operating voltage of 3 V, good rate capability and excellent cycle performance over 300 cycles. In particular, non-flammability and intrinsic self-regeneration mechanism of the inorganic liquid electrolyte presented here can accelerate the realization of commercialized Na rechargeable battery system with outstanding reliability. Given that high performance and unique properties of Na-SO2 rechargeable battery, it can be another promising candidate for next generation energy storage system.

  20. Ionic Vapor Composition in Pyridinium-Based Ionic Liquids.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

    Strong electrostatic interactions in ionic compounds make vaporization a complex process. The gas phase can contain a broad range of ionic clusters, and the cluster composition can differ greatly from that in the liquid phase. Room-temperature ionic liquids (RTILs) constitute a complicated case due to their ionic nature, asymmetric structure, and a huge versatility of ions and ionic clusters. This work reports vapor-liquid equilibria and vapor compositions of butylpyridinium (BPY) RTILs formed with hexafluorophosphate (PF6), trifluoromethanesulfonate (TF), and bis(trifluoromethanesulfonyl)imide (TFSI) anions. Unlike inorganic crystals, the pyridinium-based RTILs contain significant percentages of charged clusters in the vapor phase. Ion triplets and ion quadruplets each constitute up to 10% of the vapor phase composition. Triples prevail over quadruples in [BPY][PF6] due to the size difference of the cation and the anion. The percentage of charged ionic clusters in the gas phase is in inverse proportion to the mass of the anion. The largest identified vaporized ionic cluster comprises eight ions, with a formation probability below 1%. Higher temperature fosters formation of larger clusters due to an increase of the saturated vapor density. PMID:27165866

  1. FINAL REPORT: Room Temperature Hydrogen Storage in Nano-Confined Liquids

    SciTech Connect

    VAJO, JOHN

    2014-06-12

    DOE continues to seek solid-state hydrogen storage materials with hydrogen densities of ≥6 wt% and ≥50 g/L that can deliver hydrogen and be recharged at room temperature and moderate pressures enabling widespread use in transportation applications. Meanwhile, development including vehicle engineering and delivery infrastructure continues for compressed-gas hydrogen storage systems. Although compressed gas storage avoids the materials-based issues associated with solid-state storage, achieving acceptable volumetric densities has been a persistent challenge. This project examined the possibility of developing storage materials that would be compatible with compressed gas storage technology based on enhanced hydrogen solubility in nano-confined liquid solvents. These materials would store hydrogen in molecular form eliminating many limitations of current solid-state materials while increasing the volumetric capacity of compressed hydrogen storage vessels. Experimental methods were developed to study hydrogen solubility in nano-confined liquids. These methods included 1) fabrication of composites comprised of volatile liquid solvents for hydrogen confined within the nano-sized pore volume of nanoporous scaffolds and 2) measuring the hydrogen uptake capacity of these composites without altering the composite composition. The hydrogen storage capacities of these nano-confined solvent/scaffold composites were compared with bulk solvents and with empty scaffolds. The solvents and scaffolds were varied to optimize the enhancement in hydrogen solubility that accompanies confinement of the solvent. In addition, computational simulations were performed to study the molecular-scale structure of liquid solvent when confined within an atomically realistic nano-sized pore of a model scaffold. Confined solvent was compared with similar simulations of bulk solvent. The results from the simulations were used to formulate a mechanism for the enhanced solubility and to guide the

  2. Gallium-Based Room Temperature Liquid Metals and its Application to Single Channel Two-Liquid Hyperelastic Capacitive Strain Sensors

    NASA Astrophysics Data System (ADS)

    Liu, Shanliangzi

    Gallium-based liquid metals are of interest for a variety of applications including flexible electronics, soft robotics, and biomedical devices. Still, nano- to microscale device fabrication with these materials is challenging because of their strong adhesion to a majority of substrates. This unusual high adhesion is attributed to the formation of a thin oxide shell; however, its role in the adhesion process has not yet been established. In the first part of the thesis, we described a multiscale study aiming at understanding the fundamental mechanisms governing wetting and adhesion of gallium-based liquid metals. In particular, macroscale dynamic contact angle measurements were coupled with Scanning Electron Microscope (SEM) imaging to relate macroscopic drop adhesion to morphology of the liquid metal-surface interface. In addition, room temperature liquid-metal microfluidic devices are also attractive systems for hyperelastic strain sensing. Currently two types of liquid metal-based strain sensors exist for inplane measurements: single-microchannel resistive and two-microchannel capacitive devices. However, with a winding serpentine channel geometry, these sensors typically have a footprint of about a square centimeter, limiting the number of sensors that can be embedded into. In the second part of the thesis, firstly, simulations and an experimental setup consisting of two GaInSn filled tubes submerged within a dielectric liquid bath are used to quantify the effects of the cylindrical electrode geometry including diameter, spacing, and meniscus shape as well as dielectric constant of the insulating liquid and the presence of tubing on the overall system's capacitance. Furthermore, a procedure for fabricating the two-liquid capacitor within a single straight polydiemethylsiloxane channel is developed. Lastly, capacitance and response of this compact device to strain and operational issues arising from complex hydrodynamics near liquid-liquid and liquid

  3. Applications of ionic liquids.

    PubMed

    Patel, Divia Dinesh; Lee, Jong-Min

    2012-06-01

    Ionic liquids have recently gained popularity in the scientific community owing to their special properties and characteristics. One of the reasons why ionic liquids have been termed "green solvents" is due to their negligible vapour pressure. Their use in electrochemical, biological and metal extraction applications is discussed. Wide research has been carried out for their use in batteries, solar panels, fuel cells, drug deliveries and biomass pretreatments. This work aims to consolidate the various findings from previous works in these areas. PMID:22711528

  4. Water Contaminant Mitigation in Ionic Liquid Propellant

    NASA Technical Reports Server (NTRS)

    Conroy, David; Ziemer, John

    2009-01-01

    Appropriate system and operational requirements are needed in order to ensure mission success without unnecessary cost. Purity requirements applied to thruster propellants may flow down to materials and operations as well as the propellant preparation itself. Colloid electrospray thrusters function by applying a large potential to a room temperature liquid propellant (such as an ionic liquid), inducing formation of a Taylor cone. Ions and droplets are ejected from the Taylor cone and accelerated through a strong electric field. Electrospray thrusters are highly efficient, precise, scaleable, and demonstrate low thrust noise. Ionic liquid propellants have excellent properties for use as electrospray propellants, but can be hampered by impurities, owing to their solvent capabilities. Of foremost concern is the water content, which can result from exposure to atmosphere. Even hydrophobic ionic liquids have been shown to absorb water from the air. In order to mitigate the risks of bubble formation in feed systems caused by water content of the ionic liquid propellant, physical properties of the ionic liquid EMI-Im are analyzed. The effects of surface tension, material wetting, physisorption, and geometric details of the flow manifold and electrospray emitters are explored. Results are compared to laboratory test data.

  5. Sulfonium-based Ionic Liquids Incorporating the Allyl Functionality

    PubMed Central

    Zhao, Dongbin; Fei, Zhaofu; Ang, Wee Han; Dyson, Paul J.

    2007-01-01

    A series of sulfonium halides bearing allyl groups have been prepared and characterized. Anion metathesis with Li[Tf2N] and Ag[N(CN)2] resulted in sulfonium-based ionic liquids which exhibit low viscosities at room temperature. The solid state structure of one of the halide salts was determined by single crystal X-ray diffraction.

  6. Revisiting ether-derivatized imidazolium-based ionic liquids.

    PubMed

    Fei, Zhaofu; Ang, Wee Han; Zhao, Dongbin; Scopelliti, Rosario; Zvereva, Elena E; Katsyuba, Sergey A; Dyson, Paul J

    2007-08-30

    A series of ether-derivatized imidazolium halides have been prepared and characterized. Contrary to literature reports, they are all crystalline solids and have melting points well above room temperature (50-100 degrees C). Single crystals of the imidazolium salts, obtained in situ by slow cooling from their molten state to room temperature, were analyzed by X-ray crystallography, revealing various anion-cation interactions in the solid state. Exchange of the halides with [Tf(2)N]- yielded room temperature ionic liquids with viscosities that are comparable to related 1-alkyl-3-methylimidazolium ionic liquids. Density functional theory combined with IR spectroscopy has been used to analyze the role of functionalization of the imidazolium side chain on the formation of the molecular and supramolecular structure of the compounds and its possible impact on their physical properties. PMID:17676796

  7. Room temperature synthesized rutile TiO2 nanoparticles induced by laser ablation in liquid and their photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Liu, Peisheng; Cai, Weiping; Fang, Ming; Li, Zhigang; Zeng, Haibo; Hu, Jinlian; Luo, Xiangdong; Jing, Weiping

    2009-07-01

    TiO2 nanoparticles were prepared by one-step pulsed laser ablation of a titanium target immersed in a poly-(vinylpyrrolidone) solution at room temperature. The products were systematically characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). The results indicated that the rutile TiO2 nanocrystalline particles were one-step synthesized at room temperature and the mean size in diameter is about 50 nm with a narrow size distribution. A probable formation process was proposed on the basis of the microstructure and the instantaneous plasma plume induced by the laser. Photocatalytic activity was monitored by degradation of a methylene blue solution. The as-prepared rutile TiO2 nanoparticles demonstrate a good photocatalytic performance. This work shows that pulsed laser ablation in liquid media is a good method to synthesize some nanosized materials which are difficult to produce by other conventional methods.

  8. Ultrafast dynamics of pyrrolidinium cation ionic liquids.

    PubMed

    Shirota, Hideaki; Funston, Alison M; Wishart, James F; Castner, Edward W

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromide P1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast ( approximately 2 ps) and intermediate (approximately 20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm(-1) are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm(-1) are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape. PMID:15918734

  9. Ultrafast dynamics of pyrrolidinium cation ionic liquids

    NASA Astrophysics Data System (ADS)

    Shirota, Hideaki; Funston, Alison M.; Wishart, James F.; Castner, Edward W.

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromideP1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-,Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast (˜2ps) and intermediate (˜20ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750cm-1 are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150cm-1 are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.

  10. Phase-Changing Ionic Liquids: CO2 Capture with Ionic Liquids Involving Phase Change

    SciTech Connect

    2010-07-01

    IMPACCT Project: Notre Dame is developing a new CO2 capture process that uses special ionic liquids (ILs) to remove CO2 from the gas exhaust of coal-fired power plants. ILs are salts that are normally liquid at room temperature, but Notre Dame has discovered a new class of ILs that are solid at room temperature and change to liquid when they bind to CO2. Upon heating, the CO2 is released for storage, and the ILs re-solidify and donate some of the heat generated in the process to facilitate further CO2 release. These new ILs can reduce the energy required to capture CO2 from the exhaust stream of a coal-fired power plant when compared to state-ofthe- art technology.

  11. Ionic liquids behave as dilute electrolyte solutions

    PubMed Central

    Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

    2013-01-01

    We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

  12. VOC and HAP recovery using ionic liquids

    SciTech Connect

    Michael R. Milota : Kaichang Li

    2007-05-29

    During the manufacture of wood composites, paper, and to a lesser extent, lumber, large amounts of volatile organic compounds (VOCs) such as terpenes, formaldehyde, and methanol are emitted to air. Some of these compounds are hazardous air pollutants (HAPs). The air pollutants produced in the forest products industry are difficult to manage because the concentrations are very low. Presently, regenerative thermal oxidizers (RTOs and RCOs) are commonly used for the destruction of VOCs and HAPs. RTOs consume large amounts of natural gas to heat air and moisture. The combustion of natural gas generates increased CO2 and NOx, which have negative implications for global warming and air quality. The aforementioned problems are addressed by an absorption system containing a room-temperature ionic liquid (RTIL) as an absorbent. RTILs are salts, but are in liquid states at room temperature. RTILs, an emerging technology, are receiving much attention as replacements for organic solvents in industrial processes with significant cost and environmental benefits. Some of these processes include organic synthesis, extraction, and metal deposition. RTILs would be excellent absorbents for exhausts from wood products facilities because of their unique properties: no measurable vapor pressure, high solubility of wide range of organic compounds, thermal stability to 200°C (almost 400°F), and immisciblity with water. Room temperature ionic liquids were tested as possible absorbents. Four were imidizolium-based and were eight phosphonium-based. The imidizolium-based ionic liquids proved to be unstable at the conditions tested and in the presence of water. The phosphonium-based ionic liquids were stable. Most were good absorbents; however, cleaning the contaminates from the ionic liquids was problematic. This was overcome with a higher temperature (120°C) than originally proposed and a very low pressure (1 kPa. Absorption trials were conducted with tetradecy

  13. Electroplating Using Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Abbott, Andrew P.; Frisch, Gero; Ryder, Karl S.

    2013-07-01

    Electroplating is a key technology in many large-scale industrial applications such as corrosion-resistant and decorative coatings. Issues with current aqueous processes, such as toxicity of reagents and low current efficiencies, can often be overcome by using ionic liquids, and this approach has turned ionometallurgy into a fast-growing area of research. This review outlines the interactions in ionic liquids that are responsible for the advantageous properties of these solvents in electroplating. It summarizes recent research in which these properties have been analyzed or exploited and highlights fundamental issues in research and technology that need to be addressed.

  14. Carbenes from ionic liquids.

    PubMed

    Hollóczki, Oldamur; Nyulászi, László

    2014-01-01

    In the last decade an explosive development has been observed in the fields of both ionic liquids (ILs) as potential chemically inert solvents with many possible technical applications, and N-heterocyclic carbenes (NHCs) as catalysts with superb performance. Since the cations of many ILs can be deprotonated by strong bases yielding NHCs, this two fields are inherently connected. It has only recently been recognized that some of the commonly used basic anions of the ILs (such as acetate) are able to deprotonate azolium cations. While the resulting NHC could clearly be observed in the vapor phase, in the liquid - where the mutual electrostatic interactions within the ion network stabilize the ion pairs - the neutral NHC cannot be detected by commonly used analytical techniques; however, from these ionic liquids NHCs can be trapped, e.g., by complex formation, or more importantly these ILs can be directly used as catalysts, since the NHC content is sufficiently large for these applications. Apart from imidazole-2-ylidenes, the formation of other highly reactive neutral species ("abnormal carbenes," 2-alkylideneimidazoles, pyridine-ylidenes or pyridinium-ylides) is feasible in highly basic ionic liquids. The cross-fertilizing overlap between the two fields may provide access to a great advance in both areas, and we give an overview here on the results published so far, and also on the remaining possibilities and challenges in the concept of "carbenes from ionic liquids." PMID:23539381

  15. Surfactant-Assisted Pressurized Liquid Extraction at Room Temperature for Radix glycyrrhizae by a New Class of Surfactants.

    PubMed

    Heng, Ming Yuan; Thio, Beng Joo Reginald; Ong, Eng Shi

    2016-01-01

    A laboratory-assembled surfactant-assisted pressurized liquid extraction system at room temperature was used for the extraction of glycyrrhizin (GLY) in Radix glycyrrhizae. Environmentally friendly saccharide fatty acid ester such as glucose oleic acid ester is proposed to replace chemical-based surfactants. As the chemical properties of the surfactant obtained were unknown initially, lipase-catalyzed synthesis and liquid chromatography with tandem mass spectrometry were used to ascertain the identity. Surfactant-assisted pressurized liquid extraction (PLE) was carried out dynamically and the extraction efficiencies of the proposed method using different concentration of glucose oleic acid ester were compared with sonication using an organic solvent (ethanol/water, 70:30). The extraction efficiencies of GLY in Radix glycyrrhizae using surfactant-assisted PLE was observed to be higher compared with sonication. The method precision was found to vary from 1.3 to 5.1% (relative standard deviation, RSD, n= 6) on different days. The new method demonstrated the possibility for the extraction to be carried out at room temperature for the production of botanical extracts. PMID:26941412

  16. Importance of liquid fragility for energy applications of ionic liquids.

    PubMed

    Sippel, P; Lunkenheimer, P; Krohns, S; Thoms, E; Loidl, A

    2015-01-01

    Ionic liquids (ILs) are salts that are liquid close to room temperature. Their possible applications are numerous, e.g., as solvents for green chemistry, in various electrochemical devices, and even for such "exotic" purposes as spinning-liquid mirrors for lunar telescopes. Here we concentrate on their use for new advancements in energy-storage and -conversion devices: Batteries, supercapacitors or fuel cells using ILs as electrolytes could be important building blocks for the sustainable energy supply of tomorrow. Interestingly, ILs show glassy freezing and the universal, but until now only poorly understood dynamic properties of glassy matter, dominate many of their physical properties. We show that the conductivity of ILs, an essential figure of merit for any electrochemical application, depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility. PMID:26355037

  17. Importance of liquid fragility for energy applications of ionic liquids

    PubMed Central

    Sippel, P.; Lunkenheimer, P.; Krohns, S.; Thoms, E.; Loidl, A.

    2015-01-01

    Ionic liquids (ILs) are salts that are liquid close to room temperature. Their possible applications are numerous, e.g., as solvents for green chemistry, in various electrochemical devices, and even for such “exotic” purposes as spinning-liquid mirrors for lunar telescopes. Here we concentrate on their use for new advancements in energy-storage and -conversion devices: Batteries, supercapacitors or fuel cells using ILs as electrolytes could be important building blocks for the sustainable energy supply of tomorrow. Interestingly, ILs show glassy freezing and the universal, but until now only poorly understood dynamic properties of glassy matter, dominate many of their physical properties. We show that the conductivity of ILs, an essential figure of merit for any electrochemical application, depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility. PMID:26355037

  18. Importance of liquid fragility for energy applications of ionic liquids

    NASA Astrophysics Data System (ADS)

    Sippel, P.; Lunkenheimer, P.; Krohns, S.; Thoms, E.; Loidl, A.

    2015-09-01

    Ionic liquids (ILs) are salts that are liquid close to room temperature. Their possible applications are numerous, e.g., as solvents for green chemistry, in various electrochemical devices, and even for such “exotic” purposes as spinning-liquid mirrors for lunar telescopes. Here we concentrate on their use for new advancements in energy-storage and -conversion devices: Batteries, supercapacitors or fuel cells using ILs as electrolytes could be important building blocks for the sustainable energy supply of tomorrow. Interestingly, ILs show glassy freezing and the universal, but until now only poorly understood dynamic properties of glassy matter, dominate many of their physical properties. We show that the conductivity of ILs, an essential figure of merit for any electrochemical application, depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility.

  19. Magnetic microemulsions based on magnetic ionic liquids.

    PubMed

    Klee, Andreas; Prevost, Sylvain; Kunz, Werner; Schweins, Ralf; Kiefer, Klaus; Gradzielski, Michael

    2012-11-28

    Microemulsions with magnetic properties were formed by employing a magnetic room temperature ionic liquid (MRTIL) as polar phase, cyclohexane as oil, and an appropriate mixture of ionic surfactant and decanol as a cosurfactant. By means of small-angle neutron scattering (SANS) and electric conductivity the microemulsion structure could be confirmed, where the classical structural sequence of oil-continuous-bicontinuous-polar phase continuous is observed with increasing ratio [polar phase]/[oil]. Accordingly a maximum of the structural size is observed at about equal volumes of oil and MRTIL contained. Therefore this system is structurally the same as normal microemulsions but with the magnetic properties added to it by the incorporation into the systems formulation. PMID:23060241

  20. Homopolymer Dissolution in a Hydrophilic Ionic Liquid

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2010-03-01

    Dissolution, structure, and dynamics of both neutral and charged polymers dissolved in a hydrophilic room temperature ionic liquid (IL), ethylmethylimidazolium ethyl sulfate [EMIM][EtSO4], have been studied by classical physicochemical methods (static and dynamic light scattering, intrinsic viscosity, refractometry) to determine differences in solution behavior from conventional aqueous and organic solvents. This IL is water miscible. Many neutral polymers and charged polymer salts molecularly dissolve, although solubility doesn't correlate with polymer hydrophilicity. Model neutral soluble polymers are polyvinylpyrrolidone and hydroroxyethyl cellulose while sodium poly(styrene sulfonate) and the iodo salt of methyl-quaternized poly(vinyl pyridine) fill the same role for charged polymers. The latter display none of the polyelectrolyte effects found in low ionic strength water, consistent with strong electrostatic screening in IL. In virial coefficient and coil size, the IL acts for these neutral and charged polymers as a classical good solvent. (Support: UMass MRSEC)

  1. Dissolving Polymers in Ionic Liquids.

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2009-03-01

    Dissolution and phase behavior of polymers in ionic liquids have been assessed by solution characterization techniques such as intrinsic viscosity and light scattering (static and dynamic). Elevated viscosity proved the greatest obstacle. As yet, whether principles standard to conventional polymer solutions apply to ionic liquid solutions is uncertain, especially for polymers such as polyelectrolytes and hydrophilic block copolymers that may specifically interact with ionic liquid anions or cations. For flexible polyelectrolytes (polymers releasing counterions into high dielectric solvents), characterization in ionic liquids suggests behaviors more typical of neutral polymer. Coil sizes and conformations are approximately the same as in aqueous buffer. Further, several globular proteins dissolve in a hydrophilic ionic liquid with conformations analogous to those in buffer. General principles of solubility, however, remain unclear, making predictions of which polymer dissolves in which ionic liquid difficult; several otherwise intractable polymers (e.g., cellulose, polyvinyl alcohol) dissolve and can be efficiently functionalized in ionic liquids.

  2. Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure

    NASA Astrophysics Data System (ADS)

    Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.; Ribeiro, Mauro C. C.; Giles, Carlos

    2016-06-01

    X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114]+ and [N1444]+ proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444]+ as to [N1114]+ because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114]+ cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

  3. Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure.

    PubMed

    Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Giles, Carlos

    2016-06-14

    X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114](+) and [N1444](+) proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444](+) as to [N1114](+) because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114](+) cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids. PMID:27306015

  4. Cyclic phosphonium ionic liquids

    PubMed Central

    Mukhlall, Joshua A; Romeo, Alicia R; Gohdo, Masao; Ramati, Sharon; Berman, Marc; Suarez, Sophia N

    2014-01-01

    Summary Ionic liquids (ILs) incorporating cyclic phosphonium cations are a novel category of materials. We report here on the synthesis and characterization of four new cyclic phosphonium bis(trifluoromethylsulfonyl)amide ILs with aliphatic and aromatic pendant groups. In addition to the syntheses of these novel materials, we report on a comparison of their properties with their ammonium congeners. These exemplars are slightly less conductive and have slightly smaller self-diffusion coefficients than their cyclic ammonium congeners. PMID:24605146

  5. Wettability by Ionic Liquids.

    PubMed

    Liu, Hongliang; Jiang, Lei

    2016-01-01

    Ionic liquids (ILs) have become particularly attractive recently because they have demonstrated themselves to be important construction units in the broad fields of chemistry and materials science, from catalysis and synthesis to analysis and electrochemistry, from functional fluids to clean energy, from nanotechnology to functional materials. One of the greatest issues that determines the performance of ILs is the wettability of correlated surfaces. In this concept article, the key developments and issues in IL wettability are surveyed, including the electrowetting of ILs in gas-liquid-solid systems and liquid-liquid-solid systems, ILs as useful probe fluids, the superwettability of Ils, and future directions in IL wettability. This should generate extensive interest in the field and encourage more scientists to engage in this area to tackle its scientific challenges. PMID:26619157

  6. Ab initio molecular dynamics study of the static, dynamic, and electronic properties of liquid mercury at room temperature.

    PubMed

    Calderín, L; González, L E; González, D J

    2009-05-21

    We report a study on several static, dynamic, and electronic properties of liquid Hg at room temperature. We have performed ab initio molecular dynamics simulations using Kohn-Sham density functional theory combined with a nonlocal ultrasoft pseudopotential. The calculated static structure shows good agreement with the available experimental data. We present results for the single-particle dynamics, and recent experimental data are analyzed. The calculated dynamic structure factors S(q,omega) fairly agree with their experimental counterparts as measured by inelastic x-ray (and neutron) scattering experiments. The dispersion relation exhibits a positive dispersion, which however is not so marked as suggested by the experiment; moreover, its slope at the long-wavelength limit provides a good estimate of the experimental sound velocity. We have also analyzed the dynamical processes behind the S(q,omega) in terms of a model including a relaxation mechanism with both fast and slow characteristic time scales. PMID:19466841

  7. Properties of Water Confined in Ionic Liquids

    PubMed Central

    Saihara, Koji; Yoshimura, Yukihiro; Ohta, Soichi; Shimizu, Akio

    2015-01-01

    The varying states of water confined in the nano-domain structures of typical room temperature ionic liquids (ILs) were investigated by 1H NMR and by measurements of self-diffusion coefficients while systematically varying the IL cations and anions. The NMR peaks for water in BF4-based ILs were clearly split, indicating the presence of two discrete states of confined water (H2O and HOD). Proton and/or deuterium exchange rate among the water molecules was very slowly in the water-pocket. Notably, no significant changes were observed in the chemical shifts of the ILs. Self-diffusion coefficient results showed that water molecules exhibit a similar degree of mobility, although their diffusion rate is one order of magnitude faster than that of the IL cations and anions. These findings provide information on a completely new type of confinement, that of liquid water in soft matter. PMID:26024339

  8. Comparison studies of rheological and thermal behaviors of ionic liquids and nanoparticle ionic liquids.

    PubMed

    Xu, Yiting; Zheng, Qiang; Song, Yihu

    2015-08-14

    Novel nanoparticle ionic liquids (NILs) are prepared by grafting modified nanoparticles with long-chain ionic liquids (ILs). The NIL behaves like a liquid at ambient temperature. We studied the rheological behavior of the IL and NIL over the range of 10-55 °C and found an extraordinary difference between the IL and NIL: a small content of nanosilica (7%) moderately improves the crystallinity by 7% of the poly(ethylene glycol) (PEG) segment in the IL, and it improves the dynamic moduli significantly (by 5 times at room temperature). It retards the decay temperature (by 10 °C) of the dynamic moduli during heating as well. The thermal rheological hysteresis observed during heating-cooling temperature sweeps is ascribed to the melting-recrystallization of the PEG segments. Meanwhile, the IL and NIL express accelerated crystallization behavior in comparison with the oligomeric anion. For the first time, we find that ILs and NILs are able to form nanoparticle-containing spherulites at room temperature after long time aging. PMID:26156247

  9. Room temperature compressibility and diffusivity of liquid water from first principles.

    PubMed

    Corsetti, Fabiano; Artacho, Emilio; Soler, José M; Alexandre, S S; Fernández-Serra, M-V

    2013-11-21

    The isothermal compressibility of water is essential to understand its anomalous properties. We compute it by ab initio molecular dynamics simulations of 200 molecules at five densities, using two different van der Waals density functionals. While both functionals predict compressibilities within ~30% of experiment, only one of them accurately reproduces, within the uncertainty of the simulation, the density dependence of the self-diffusion coefficient in the anomalous region. The discrepancies between the two functionals are explained in terms of the low- and high-density structures of the liquid. PMID:24320334

  10. Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

    SciTech Connect

    Gering, Kevin L.; Harrup, Mason K.; Rollins, Harry W.

    2015-12-08

    An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

  11. Enzyme catalysis in ionic liquids.

    PubMed

    Kragl, Udo; Eckstein, Marrit; Kaftzik, Nicole

    2002-12-01

    Ionic liquids offer new possibilities for the application of solvent engineering to biocatalytic reactions. Although in many cases ionic liquids have simply been used to replace organic solvents, they have often led to improved process performance. Unlike conventional organic solvents, ionic liquids possess no vapor pressure, are able to dissolve many compounds, and can be used to form two-phase systems with many solvents. To date, reactions involving lipases have benefited most from the use of ionic liquids, but the use of ionic liquids with other enzymes and in whole-cell processes has also been described. In some cases, remarkable results with respect to yield, (enantio)selectivity or enzyme stability were observed. PMID:12482515

  12. Electrodeposition in Ionic Liquids.

    PubMed

    Zhang, Qinqin; Wang, Qian; Zhang, Suojiang; Lu, Xingmei; Zhang, Xiangping

    2016-02-01

    Due to their attractive physico-chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template-assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air- and water-stable ILs, deep eutectic solvents (DESs), ILs with metal-containing cations, and protic ILs. Template-assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted. PMID:26530378

  13. Low-melting mixtures based on choline ionic liquids.

    PubMed

    Rengstl, Doris; Fischer, Veronika; Kunz, Werner

    2014-11-01

    In this article a strategy is proposed for the design of low toxic, room temperature liquid low-melting mixtures (LMMs) which are entirely composed of natural materials. From literature it is well known that, in general, deep eutectic solvents based on choline chloride and dicarboxylic acids are LMMs, but not liquids at room temperature, with one exception: a 1 : 1 molar mixture of malonic acid and choline chloride. Therefore, the starting point of this study was the decrease of the melting point of one of the components, namely the dicarboxylic acid, which is succinic, glutaric or adipic acid. For this purpose, one of the two protons of the acidic group was exchanged by a bulky unsymmetrical choline cation. The resulting ionic liquids (ILs) were still solid at room temperature, but have a reduced melting temperature compared to the corresponding acids. In the second step, mixtures of these ILs with choline chloride were prepared. It turned out that choline glutarate-choline chloride mixtures are liquids at room temperature at compositions containing 95-98 wt% of choline glutarate. Finally, urea was added as another hydrogen bond donor. Density, conductivity and viscosity measurements were performed for all obtained mixtures. Moreover, a Walden plot was drawn which indicates that all mixtures are liquids with fully dissociated ions moving independently. Therefore, they are considered as "good" ionic liquids and, thus, for example they can be used to exchange more toxic or less biodegradable ILs in application processes. A brief outlook containing application possibilities is given. It is demonstrated that choline dodecylsulfate is readily soluble in these mixtures, forming aggregates in the LMM at temperatures exceeding 55 °C. PMID:25242504

  14. Room temperature deposition of ZnSe thin films by successive ionic layer adsorption and reaction (SILAR) method

    SciTech Connect

    Kale, R.B.; Lokhande, C.D. . E-mail: rb_kale@yahoo.co.in

    2004-10-04

    The zinc selenide (ZnSe) thin films are deposited onto glass substrate using relatively simple and inexpensive successive ionic layer adsorption and reaction (SILAR) method. The films are deposited using zinc acetate sodium selenosulphate precursors. The concentration, pH, immersion and rinsing times and number of immersion cycles have been optimized to obtain good quality ZnSe thin films. The X-ray diffraction (XRD) study and scanning electron microscopy (SEM) studies reveals nanocrystalline nature alongwith some amorphous phase present in ZnSe thin films. Energy dispersive X-ray (EDAX) analysis shows that the films are Se deficient. From optical absorption data, the optical band gap 'E{sub g}' for as-deposited thin film was found to be 2.8 eV and electrical resistivity in the order of 10{sup 7} {omega} cm.

  15. Morphology-induced low temperature conductivity in ionic liquids

    NASA Astrophysics Data System (ADS)

    Erbas, Aykut; Olvera de La Cruz, Monica; Olvera de la Cruz Team

    Ionic liquids exhibit nano-scale liquid crystalline order depending on the polymeric details of salt molecules. The resulting morphology and temperature behavior are key factors in determining the room temperature conductivity of ionic liquids. Here we discuss the phase behavior and related ionic conductivities of dry ionic liquids with volume fractions close to unity by using extensive molecular dynamics simulations. Temperature dependence, effective persistence length of tails, and excluded volume symmetry of amphiphilic ionic liquid molecules are investigated in large scale systems with short and long-range electrostatics. Our results suggest that by adjusting stiffness of the amphiphilic molecules and excluded volume interactions, lamellar or interconnected 3D phases can be obtained. Resulting phases have significant effects on the conductive properties. If there is no excluded volume asymmetry along the molecules, mostly lamellar phases with anisotropic conductivities emerge. If the excluded volume interactions become asymmetric, lamellar phases are replaced by interconnected phases consist of charged groups. Within temperature ranges that morphological phases are observed, conductivities exhibit low-temperature maxima in accord with experiments of ionic liquid-based liquid Center of Bio-inspried Energy Center (CBES).

  16. Liquid-liquid extraction of neodymium(III) by dialkylphosphate ionic liquids from acidic medium: the importance of the ionic liquid cation.

    PubMed

    Rout, Alok; Kotlarska, Justyna; Dehaen, Wim; Binnemans, Koen

    2013-10-21

    The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity. PMID:23949284

  17. A New Class of Ionic Liquids: Anion Amphiprotic Ionic Liquids.

    PubMed

    Treskow, Marcel; Pitawala, Jagath; Arenz, Sven; Matic, Aleksandar; Johansson, Patrik

    2012-08-16

    We here present a new class of protic ionic liquids, anion amphiprotic ionic liquids (AAILs). These materials are protonation equilibrium free protic ionic liquids and interesting in their own right by not following the classical Brønsted acid-base neutralization concept. Due to the very simple synthesis route applied and their stable basic chemistry, we believe in a potential use for manifold applications. This is supported by the combination of practical material properties, foremost, a general intrinsic stability versus reversal of the formation reaction toward neutral species, broad liquidus ranges, long-term thermal stabilities, high conductivities, protic characteristics, and a general stability versus water. PMID:26295756

  18. Effective Energy Transfer via Plasmon-Activated High-Energy Water Promotes Its Fundamental Activities of Solubility, Ionic Conductivity, and Extraction at Room Temperature

    NASA Astrophysics Data System (ADS)

    Yang, Chih-Ping; Chen, Hsiao-Chien; Wang, Ching-Chiung; Tsai, Po-Wei; Ho, Chia-Wen; Liu, Yu-Chuan

    2015-12-01

    Water is a ubiquitous solvent in biological, physical, and chemical processes. Unique properties of water result from water’s tetrahedral hydrogen-bonded (HB) network (THBN). The original THBN is destroyed when water is confined in a nanosized environment or localized at interfaces, resulting in corresponding changes in HB-dependent properties. In this work, we present an innovative idea to validate the reserve energy of high-energy water and applications of high-energy water to promote water’s fundamental activities of solubility, ionic conductivity, and extraction at room temperature. High-energy water with reduced HBs was created by utilizing hot electrons with energies from the decay of surface plasmon excited at gold (Au) nanoparticles (NPs). Compared to conventional deionized (DI) water, solubilities of alkali metal-chloride salts in high-energy water were significantly increased, especially for salts that release heat when dissolved. The ionic conductivity of NaCl in high-energy water was also markedly higher, especially when the electrolyte’s concentration was extremely low. In addition, antioxidative components, such as polyphenols and 2,3,5,4’-tetrahydroxystilbene-2-O-beta-d-glucoside (THSG) from teas, and Polygonum multiflorum (PM), could more effectively be extracted using high-energy water. These results demonstrate that high-energy water has emerged as a promising innovative solvent for promoting water’s fundamental activities via effective energy transfer.

  19. Effective Energy Transfer via Plasmon-Activated High-Energy Water Promotes Its Fundamental Activities of Solubility, Ionic Conductivity, and Extraction at Room Temperature.

    PubMed

    Yang, Chih-Ping; Chen, Hsiao-Chien; Wang, Ching-Chiung; Tsai, Po-Wei; Ho, Chia-Wen; Liu, Yu-Chuan

    2015-01-01

    Water is a ubiquitous solvent in biological, physical, and chemical processes. Unique properties of water result from water's tetrahedral hydrogen-bonded (HB) network (THBN). The original THBN is destroyed when water is confined in a nanosized environment or localized at interfaces, resulting in corresponding changes in HB-dependent properties. In this work, we present an innovative idea to validate the reserve energy of high-energy water and applications of high-energy water to promote water's fundamental activities of solubility, ionic conductivity, and extraction at room temperature. High-energy water with reduced HBs was created by utilizing hot electrons with energies from the decay of surface plasmon excited at gold (Au) nanoparticles (NPs). Compared to conventional deionized (DI) water, solubilities of alkali metal-chloride salts in high-energy water were significantly increased, especially for salts that release heat when dissolved. The ionic conductivity of NaCl in high-energy water was also markedly higher, especially when the electrolyte's concentration was extremely low. In addition, antioxidative components, such as polyphenols and 2,3,5,4'-tetrahydroxystilbene-2-O-beta-d-glucoside (THSG) from teas, and Polygonum multiflorum (PM), could more effectively be extracted using high-energy water. These results demonstrate that high-energy water has emerged as a promising innovative solvent for promoting water's fundamental activities via effective energy transfer. PMID:26658304

  20. Effective Energy Transfer via Plasmon-Activated High-Energy Water Promotes Its Fundamental Activities of Solubility, Ionic Conductivity, and Extraction at Room Temperature

    PubMed Central

    Yang, Chih-Ping; Chen, Hsiao-Chien; Wang, Ching-Chiung; Tsai, Po-Wei; Ho, Chia-Wen; Liu, Yu-Chuan

    2015-01-01

    Water is a ubiquitous solvent in biological, physical, and chemical processes. Unique properties of water result from water’s tetrahedral hydrogen-bonded (HB) network (THBN). The original THBN is destroyed when water is confined in a nanosized environment or localized at interfaces, resulting in corresponding changes in HB-dependent properties. In this work, we present an innovative idea to validate the reserve energy of high-energy water and applications of high-energy water to promote water’s fundamental activities of solubility, ionic conductivity, and extraction at room temperature. High-energy water with reduced HBs was created by utilizing hot electrons with energies from the decay of surface plasmon excited at gold (Au) nanoparticles (NPs). Compared to conventional deionized (DI) water, solubilities of alkali metal-chloride salts in high-energy water were significantly increased, especially for salts that release heat when dissolved. The ionic conductivity of NaCl in high-energy water was also markedly higher, especially when the electrolyte’s concentration was extremely low. In addition, antioxidative components, such as polyphenols and 2,3,5,4’-tetrahydroxystilbene-2-O-beta-d-glucoside (THSG) from teas, and Polygonum multiflorum (PM), could more effectively be extracted using high-energy water. These results demonstrate that high-energy water has emerged as a promising innovative solvent for promoting water’s fundamental activities via effective energy transfer. PMID:26658304

  1. Synthesis and characterization of new class of ionic liquids containing phenolate anion

    SciTech Connect

    Lethesh, Kallidanthiyil Chellappan; Wilfred, Cecilia Devi; Taha, M. F.; Thanabalan, M.

    2014-10-24

    In these manuscript novel ionic liquids containing a new class of 'phenolate' anions was synthesized and characterized. 1-methylmidazole with different alkyl chains such as butyl, hexyl and octyl groups was used as the cationic part. All the ionic liquids were obtained as liquids at room temperature. The synthesized ionic liquids were characterized using {sup 1}H NMR and {sup 13}C NMR spectroscopy. The thermal stability of the ionic liquids was studied using thermo gravimetric analysis (TGA). The effect of temperature on the density and viscosity of the ionic liquids were studied over a temperature range from 293.15 K to 373.15K at atmospheric pressure. From the experimental values of density, the molecular volume, standard molar entropy and the lattice energy of the ionic liquids were calculated.

  2. Ionic Liquids with Ammonium Cations as Lubricants or Additives

    SciTech Connect

    Qu, Jun; Blau, Peter Julian; Dai, Sheng; Luo, Huimin; Truhan, Jr., John J

    2006-01-01

    Friction and wear are estimated to cost 6% of the US gross national product, or around $700 billion annually. A new class of more effective lubricants could lead to huge energy savings. Limited recent literature has suggested potential for using room-temperature ionic liquids as lubricants, however only a few out of millions (or more) of species have been evaluated. Recent ORNL work discovered a new category of ionic liquids with ammonium cations that have demonstrated promising lubricating properties as net lubricants or lubricant additives, particularly in lubricating difficult-to-lubricate metals like aluminum. More than 30% friction reduction has been observed on ammonium-based ionic liquids compared to conventional hydrocarbon oils. The inherent polarity of ionic liquids is believed to provide strong adhesion to contact surfaces and form a boundary lubricating film leading to friction and wear reductions. Other advantages of ionic liquids include (1) negligible volatility, (2) high thermal stability, (3) non-flammability, and (4) better intrinsic properties that eliminate the necessity of many expensive lubricant additives. With very flexible molecular structures, this new class of lubricants, particularly ammonium-based ionic liquids, can be tailored to fit a big variety of applications including but not limited to bearings, combustion engines, MEMS, and metal forming.

  3. Novel applications of ionic liquids in materials processing

    NASA Astrophysics Data System (ADS)

    Reddy, Ramana G.

    2009-05-01

    Ionic liquids are mixtures of organic and inorganic salts which are liquids at room temperature. Several potential applications of ionic liquids in the field of materials processing are electrowinning and electrodeposition of metals and alloys, electrolysis of active metals at low temperature, liquid-liquid extraction of metals. Results using 1-butyl-3-methylimidazolium chloride with AlCl3 at low temperatures yielded high purity aluminium deposits (>99.9% pure) and current efficiencies >98%. Titanium and aluminium were co-deposited with/without the addition of TiCl4 with up to 27 wt% Ti in the deposit with current efficiencies in the range of 78-85 %. Certain ionic liquids are potential replacements for thermal oils and molten salts as heat transfer fluids in solar energy applications due to high thermal stability, very low corrosivity and substantial sensible heat retentivity. The calculated storage densities for several chloride and fluoride ionic liquids are in the range of 160-210 MJ/m3. A 3-D mathematical model was developed to simulate the large scale electrowinning of aluminium. Since ionic liquids processing results in their low energy consumption, low pollutant emissions many more materials processing applications are expected in future.

  4. Ionic liquid of a gold nanocluster: a versatile matrix for electrochemical biosensors.

    PubMed

    Kwak, Kyuju; Kumar, S Senthil; Pyo, Kyunglim; Lee, Dongil

    2014-01-28

    Ionic liquids are room-temperature molten salts that are increasingly used in electrochemical devices, such as batteries, fuel cells, and sensors, where their intrinsic ionic conductivity is exploited. Here we demonstrate that combining anionic, redox-active Au25 clusters with imidazolium cations leads to a stable ionic liquid possessing both ionic and electronic conductivity. The Au25 ionic liquid was found to act as a versatile matrix for amperometric enzyme biosensors toward the detection of glucose. Enzyme electrodes prepared by incorporating glucose oxidase in the Au25 ionic liquid show high electrocatalytic activity and substrate affinity. Au25 clusters in the electrode were found to act as effective redox mediators as well as electronic conductors determining the detection sensitivity. With the unique electrochemical properties and almost unlimited structural tunability, the ionic liquids of quantum-sized gold clusters may serve as versatile matrices for a variety of electrochemical biosensors. PMID:24350837

  5. Hydrophobic ionic liquids

    DOEpatents

    Koch, V.R.; Nanjundiah, C.; Carlin, R.T.

    1998-10-27

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas shown in a diagram wherein R{sub 1}, R{sub 2}, R{sub 3}, R{sub 4}, R{sub 5}, and R{sub 6} are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F-, Cl-, CF{sub 3}-, SF{sub 5}-, CF{sub 3}S-, (CF{sub 3}){sub 2}CHS- or (CF{sub 3}){sub 3}CS-; and X{sup {minus}} is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 {angstrom}{sup 3}. 4 figs.

  6. Hydrophobic ionic liquids

    DOEpatents

    Koch, Victor R.; Nanjundiah, Chenniah; Carlin, Richard T.

    1998-01-01

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F--, Cl--, CF.sub.3 --, SF.sub.5 --, CF.sub.3 S--, (CF.sub.3).sub.2 CHS-- or (CF.sub.3).sub.3 CS--; and X.sup.- is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 .ANG..sup.3.

  7. Limitations to the room temperature mobility of two- and three-dimensional electron liquids in SrTiO{sub 3}

    SciTech Connect

    Mikheev, Evgeny; Himmetoglu, Burak; Kajdos, Adam P.; Moetakef, Pouya; Cain, Tyler A.; Van de Walle, Chris G.; Stemmer, Susanne

    2015-02-09

    We analyze and compare the temperature dependence of the electron mobility of two- and three-dimensional electron liquids in SrTiO{sub 3}. The contributions of electron-electron scattering must be taken into account to accurately describe the mobility in both cases. For uniformly doped, three-dimensional electron liquids, the room temperature mobility crosses over from longitudinal optical (LO) phonon-scattering-limited to electron-electron-scattering-limited as a function of carrier density. In high-density, two-dimensional electron liquids, LO phonon scattering is completely screened and the mobility is dominated by electron-electron scattering up to room temperature. The possible origins of the observed behavior and the consequences for approaches to improve the mobility are discussed.

  8. Ionic Liquid Crystals: Versatile Materials.

    PubMed

    Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

    2016-04-27

    This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions. PMID:27088310

  9. Ionic Liquid Epoxy Resin Monomers

    NASA Technical Reports Server (NTRS)

    Paley, Mark S. (Inventor)

    2013-01-01

    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  10. Ionic Liquid Membranes for Carbon Dioxide Separation

    SciTech Connect

    Myers, C.R.; Ilconich, J.B.; Luebke, D.R.; Pennline, H.W.

    2008-07-12

    Recent scientific studies are rapidly advancing novel technological improvements and engineering developments that demonstrate the ability to minimize, eliminate, or facilitate the removal of various contaminants and green house gas emissions in power generation. The Integrated Gasification Combined Cycle (IGCC) shows promise for carbon dioxide mitigation not only because of its higher efficiency as compared to conventional coal firing plants, but also due to a higher driving force in the form of high partial pressure. One of the novel technological concepts currently being developed and investigated is membranes for carbon dioxide (CO2) separation, due to simplicity and ease of scaling. A challenge in using membranes for CO2 capture in IGCC is the possibility of failure at elevated temperatures or pressures. Our earlier research studies examined the use of ionic liquids on various supports for CO2 separation over the temperature range, 37°C-300°C. The ionic liquid, 1-hexyl-3methylimidazolium Bis(trifluoromethylsulfonyl)imide, ([hmim][Tf2N]), was chosen for our initial studies with the following supports: polysulfone (PSF), poly(ether sulfone) (PES), and cross-linked nylon. The PSF and PES supports had similar performance at room temperature, but increasing temperature caused the supported membranes to fail. The ionic liquid with the PES support greatly affected the glass transition temperature, while with the PSF, the glass transition temperature was only slightly depressed. The cross-linked nylon support maintained performance without degradation over the temperature range 37-300°C with respect to its permeability and selectivity. However, while the cross-linked nylon support was able to withstand temperatures, the permeability continued to increase and the selectivity decreased with increasing temperature. Our studies indicated that further testing should examine the use of other ionic liquids, including those that form chemical complexes with CO2 based on

  11. Glass transition of ionic liquids under high pressure

    NASA Astrophysics Data System (ADS)

    Ribeiro, Mauro C. C.; Pádua, Agílio A. H.; Gomes, Margarida F. Costa

    2014-06-01

    The glass transition pressure at room temperature, pg, of six ionic liquids based on 1-alkyl-3-methylimidazolium cations and the anions [BF4]-, [PF6]-, and bis(trifluromethanesulfonyl)imide, [NTf2]-, has been obtained from the pressure dependence of the bandwidth of the ruby fluorescence line in diamond anvil cells. Molar volume, Vm(pg), has been estimated by a group contribution model (GCM) developed for the ionic liquids. A density scaling relation, TVγ, has been considered for the states Vm(pg, 295 K) and Vm(Tg, 0.1 MPa) using the simplifying condition that the viscosity at the glass transition is the same at pg at room temperature and at atmospheric pressure at Tg. Assuming a constant γ over this range of density, a reasonable agreement has been found for the γ determined herein and that of a previous density scaling analysis of ionic liquids viscosities under moderate conditions. Further support for the appropriateness of extrapolating the GCM equation of state to the GPa pressure range is provided by comparing the GCM and an equation of state previously derived in the power law density-scaling regime.

  12. Selective extraction of copper, mercury, silver and palladium ionsfrom water using hydrophobic ionic liquids.

    SciTech Connect

    Papaiconomou, Nicolas; Lee, Jong-Min; Salminen, Justin; VonStosch, Moritz; Prausnitz, John M.

    2007-06-25

    Extraction of dilute metal ions from water was performed near room temperature with a variety of ionic liquids. Distribution coefficients are reported for fourteen metal ions extracted with ionic liquids containing cations 1-octyl-4-methylpyridinium [4MOPYR]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPYRRO]{sup +} or 1-methyl-1-octylpiperidinium [MOPIP]{sup +}, and anions tetrafluoroborate [BF{sub 4}]{sup +}, trifluoromethyl sulfonate [TfO]{sup +} or nonafluorobutyl sulfonate [NfO]{sup +}. Ionic liquids containing octylpyridinium cations are very good for extracting mercury ions. However, other metal ions were not significantly extracted by any of these ionic liquids. Extractions were also performed with four new task-specific ionic liquids. Such liquids containing a disulfide functional group are efficient and selective for mercury and copper, whereas those containing a nitrile functional group are efficient and selective for silver and palladium.

  13. Excitation-energy dependence of solvation dynamics in room-temperature ionic liquids.

    PubMed

    Kim, Daekeon; Park, Sang-Won; Shim, Youngseon; Kim, Hyung J; Jung, YounJoon

    2016-07-28

    Influence of the excitation energy of a probe solute molecule on its solvation dynamics and emission spectrum in 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI(+)PF6 (-)) is studied via molecular dynamics simulations using a coarse-grained model description. By exciting the probe at different energies, each with an extremely narrow distribution, ensuing solvent relaxation and its dynamic variance are monitored using the isoconfigurational ensemble method. Resulting Stokes shift function, S(t), indicates that long-time solvent relaxation becomes slower with the decreasing excitation energy and approaches the equilibrium correlation function, C(t), of solvent fluctuations. This suggests that the system excited at the red-edge of the spectrum observes linear response better than that at the blue-edge. A detailed analysis of nonequilibrium trajectories shows that the effect of initial configurations on variance of relaxation dynamics is mainly confined to short times; it reaches a maximum around 0.1 ≲ t ≲ 1 ps and diminishes as time further increases. The influence of the initial velocity distribution, on the other hand, tends to grow with time and dominates the long-time variations of dynamics. The emission spectrum shows the red-edge effect in accord with previous studies. PMID:27475376

  14. Excitation-energy dependence of solvation dynamics in room-temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Kim, Daekeon; Park, Sang-Won; Shim, Youngseon; Kim, Hyung J.; Jung, YounJoon

    2016-07-01

    Influence of the excitation energy of a probe solute molecule on its solvation dynamics and emission spectrum in 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI+PF6-) is studied via molecular dynamics simulations using a coarse-grained model description. By exciting the probe at different energies, each with an extremely narrow distribution, ensuing solvent relaxation and its dynamic variance are monitored using the isoconfigurational ensemble method. Resulting Stokes shift function, S(t), indicates that long-time solvent relaxation becomes slower with the decreasing excitation energy and approaches the equilibrium correlation function, C(t), of solvent fluctuations. This suggests that the system excited at the red-edge of the spectrum observes linear response better than that at the blue-edge. A detailed analysis of nonequilibrium trajectories shows that the effect of initial configurations on variance of relaxation dynamics is mainly confined to short times; it reaches a maximum around 0.1 ≲ t ≲ 1 ps and diminishes as time further increases. The influence of the initial velocity distribution, on the other hand, tends to grow with time and dominates the long-time variations of dynamics. The emission spectrum shows the red-edge effect in accord with previous studies.

  15. Room-Temperature Ionic Liquids and Protective Phospholipid Membranes: Interactions on Surfaces

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Green chemistry is a growing area of research that involves reducing or eliminating hazardous materials (products and solvents) from chemical processes. An area of green chemistry that is quite interesting to us is bioelectrocatalytic transformation of lipids in non-aqueous solvents called room-tem...

  16. Room-temperature ionic liquids: temperature dependence of gas solubility selectivity

    SciTech Connect

    Alexia Finotello; Jason E. Bara; Dean Camper; Richard D. Noble

    2008-05-15

    This study focuses on bulk fluid solubility of carbon dioxide (CO{sub 2}), methane (CH{sub 4}), hydrogen (H{sub 2}), and nitrogen (N{sub 2}) gases in the imidazolium-based RTILs: 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((emim)(Tf{sub 2}N)),1-ethyl-3-methylimidazolium tetrafluoroborate ((emim)(BF{sub 4})),1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide((hmim)(Tf{sub 2}N)), and 1,3-dimethylimidazolium methyl sulfate ((mmim)(MeSO{sub 4})) as a function of temperature (25, 40, 55, and 70{sup o}C) at near-atmospheric pressures. The experimental behaviors are explained in terms of thermodynamic relationships that account for the negligible vapor pressure of the RTIL as well as the low solubilities of the gases. Results show that, as temperature increases, the solubility of CO{sub 2} decreases in all RTILs, the solubility of CH{sub 4} remains constant in (emim)(Tf{sub 2}N) and (hmim)(Tf{sub 2}N) but increases in(mmim)(MeSO{sub 4}) and (emim)(BF{sub 4}), and the solubility of N{sub 2} and H{sub 2} increases. Also, the ideal solubility selectivity (ratio of pure-component solubilities) increases as temperature decreases for CO{sub 2}/N{sub 2}, CO{sub 2}/CH{sub 4}, and CO{sub 2}/H{sub 2} systems. Experimental values for the enthalpy and entropy of solvation are reported.

  17. Solidlike coherent vibronic dynamics in a room temperature liquid: Resonant Raman and absorption spectroscopy of liquid bromine

    NASA Astrophysics Data System (ADS)

    Branigan, Edward T.; van Staveren, Marie N.; Apkarian, V. Ara

    2010-01-01

    UV-visible absorption and resonance Raman (RR) spectra of liquid bromine are presented and rigorously interpreted. The RR spectra, which show an anharmonic vibrational progression of up to 30 overtones, define the ground state potential in the range 2.05 Åliquid phase, indicating an attractive cage-molecule interaction. The excited state potentials (A', B, and C) are extracted from the absorption spectrum. The spectrum is first inverted under assumption of the classical reflection approximation, then corrected by forward simulations through quantum time correlations. The extrapolated B and C potentials are used to simulate RR spectra. Their validity is cross-checked by the interference pattern of the polarized spectra due to two-channel RR scattering. The discrepancy between calculated and observed intensities can be entirely assigned to vibrational dephasing, which is observed to follow the exponential energy gap law—dephasing rates perfectly trace the Birge-Sponer plot of the vibrational progression—suggesting that vibrational dissipation controls the decay of coherence. Despite strong intermolecular electronic interactions and vibrational energy gaps of ˜kT, vibrational coherences are long lived: Coherence times range from ≥25 to ≥2.4 ps between v =1 and v =25. Remarkably, the RR line shapes are skewed toward the red, indicating upchirp in frequencies that develop over a period of 400 fs. Evidently, the molecular vibrations adiabatically follow the solvent cage, which is impulsively driven into expansion during the ˜20 fs evolution on the electronically excited state. Liquid bromine retains coherence in ordered sluggish local cages with quadrupolar interactions—dynamics akin to molecules isolated in structured cryogenic rare gas solids.

  18. Particle aggregation mechanisms in ionic liquids.

    PubMed

    Szilagyi, Istvan; Szabo, Tamas; Desert, Anthony; Trefalt, Gregor; Oncsik, Tamas; Borkovec, Michal

    2014-05-28

    Aggregation of sub-micron and nano-sized polystyrene latex particles was studied in room temperature ionic liquids (ILs) and in their water mixtures by time-resolved light scattering. The aggregation rates were found to vary with the IL-to-water molar ratio in a systematic way. At the water side, the aggregation rate is initially small, but increases rapidly with increasing IL content, and reaches a plateau value. This behaviour resembles simple salts, and can be rationalized by the competition of double-layer and van der Waals forces as surmised by the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). At the IL side, aggregation slows down again. Two generic mechanisms could be identified to be responsible for the stabilization in ILs, namely viscous stabilization and solvation stabilization. Viscous stabilization is important in highly viscous ILs, as it originates from the slowdown of the diffusion controlled aggregation due to the hindrance of the diffusion in a viscous liquid. The solvation stabilization mechanism is system specific, but can lead to a dramatic slowdown of the aggregation rate in ILs. This mechanism is related to repulsive solvation forces that are operational in ILs due to the layering of the ILs close to the surfaces. These two stabilization mechanisms are suspected to be generic, as they both occur in different ILs, and for particles differing in surface functionalities and size. PMID:24727976

  19. Efficient and green synthesis of tetrasubstituted pyrroles promoted by task-specific basic ionic liquids as catalyst in aqueous media.

    PubMed

    Yavari, Issa; Kowsari, Elaheh

    2009-11-01

    Synthesis of tetrasubstituted pyrroles by the three-component condensation reaction of acid chlorides, dialkyl acetylenedicarboxylates, and amino acids in the presence of various room-temperature ionic liquids (RTILs) as catalysts in water is reported. Among the ionic liquids used, the basic functionalized ionic liquid, butyl methyl imidazolium hydroxide [bmim]OH, was the most effective catalyst. The influence of reaction temperature, reaction time, and amount of ionic liquid on the reaction was investigated. The [bmim]OH/H(2)O catalyst system could be reused for at least five recycles without appreciable loss of efficiency. PMID:19381850

  20. Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Tigelaar, Dean M.

    2009-01-01

    Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

  1. Ionic liquids and their solid-state analogues as materials for energy generation and storage

    NASA Astrophysics Data System (ADS)

    Macfarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.; Kar, Mega; Passerini, Stefano; Pringle, Jennifer M.; Ohno, Hiroyuki; Watanabe, Masayoshi; Yan, Feng; Zheng, Wenjun; Zhang, Shiguo; Zhang, Jie

    2016-02-01

    Salts that are liquid at room temperature, now commonly called ionic liquids, have been known for more than 100 years; however, their unique properties have only come to light in the past two decades. In this Review, we examine recent work in which the properties of ionic liquids have enabled important advances to be made in sustainable energy generation and storage. We discuss the use of ionic liquids as media for synthesis of electromaterials, for example, in the preparation of doped carbons, conducting polymers and intercalation electrode materials. Focusing on their intrinsic ionic conductivity, we examine recent reports of ionic liquids used as electrolytes in emerging high-energy-density and low-cost batteries, including Li-ion, Li-O2, Li-S, Na-ion and Al-ion batteries. Similar developments in electrolyte applications in dye-sensitized solar cells, thermo-electrochemical cells, double-layer capacitors and CO2 reduction are also discussed.

  2. Ionic-liquid materials for the electrochemical challenges of the future.

    PubMed

    Armand, Michel; Endres, Frank; MacFarlane, Douglas R; Ohno, Hiroyuki; Scrosati, Bruno

    2009-08-01

    Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges. PMID:19629083

  3. Stable and water-tolerant ionic liquid ferrofluids.

    PubMed

    Jain, Nirmesh; Zhang, Xiaoli; Hawkett, Brian S; Warr, Gregory G

    2011-03-01

    Ionic liquid ferrofluids have been prepared containing both bare and sterically stabilized 8-12 nm diameter superparamagnetic iron oxide nanoparticles, which remain stable for several months in both protic ethylammonium and aprotic imidazolium room-temperature ionic liquids. These ferrofluids exhibit spiking in static magnetic fields similar to conventional aqueous and nonaqueous ferrofluids. Ferrofluid stability was verified by following the flocculation and settling behavior of dilute nanoparticle dispersions. Although bare nanoparticles showed excellent stability in some ILs, they were unstable in others, and exhibited limited water tolerance. Stability was achieved by incorporating a thin polymeric steric stabilization layer designed to be compatible with the IL. This confers the added benefit of imbuing the ILF with a high tolerance to water. PMID:21338083

  4. Nanoparticle enhanced ionic liquid heat transfer fluids

    DOEpatents

    Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.; Gray, Joshua R.; Garcia-Diaz, Brenda L.

    2014-08-12

    A heat transfer fluid created from nanoparticles that are dispersed into an ionic liquid is provided. Small volumes of nanoparticles are created from e.g., metals or metal oxides and/or alloys of such materials are dispersed into ionic liquids to create a heat transfer fluid. The nanoparticles can be dispersed directly into the ionic liquid during nanoparticle formation or the nanoparticles can be formed and then, in a subsequent step, dispersed into the ionic liquid using e.g., agitation.

  5. The hype with ionic liquids as solvents

    NASA Astrophysics Data System (ADS)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

    In this mini review, we give our personal opinion about the present state of the art concerning Ionic Liquids, proposed as alternative solvents. In particular, we consider their different drawbacks and disadvantages and discuss the critical aspects of the research of Ionic Liquids as solvents. Finally, we point out some aspects on potentially promising Ionic Liquid solvents.

  6. Low Temperature Reduction of Alumina Using Fluorine Containing Ionic Liquids

    SciTech Connect

    Reddy, Ramana

    2009-01-31

    EXECUTIVE SUMMARY The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient

  7. Low Temperature Reduction of Alumina Using Fluorine Containing Ionic Liquids

    SciTech Connect

    Dr. R. G. Reddy

    2007-09-01

    The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient (0.40). Nucleation

  8. Low Temperature Reduction of Alumina Using Fluorine Containing Ionic Liquids

    SciTech Connect

    Reddy, Ramana G

    2009-01-31

    EXECUTIVE SUMMARY The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer

  9. Pressure and temperature effects on intermolecular vibrational dynamics of ionic liquids.

    PubMed

    Penna, Tatiana C; Faria, Luiz F O; Matos, Jivaldo R; Ribeiro, Mauro C C

    2013-03-14

    Low frequency Raman spectra of ionic liquids have been obtained as a function of pressure up to ca. 4.0 GPa at room temperature and as a function of temperature along the supercooled liquid and glassy state at atmospheric pressure. Intermolecular vibrations are observed at ~20, ~70, and ~100 cm(-1) at room temperature in ionic liquids based on 1-alkyl-3-methylimidazolium cations. The component at ~100 cm(-1) is assigned to librational motion of the imidazolium ring because it is absent in non-aromatic ionic liquids. There is a correspondence between the position of intermolecular vibrational modes in the normal liquid state and the spectral features that the Raman spectra exhibit after partial crystallization of samples at low temperatures or high pressures. The pressure-induced frequency shift of the librational mode is larger than the other two components that exhibit similar frequency shifts. The lowest frequency vibration observed in a glassy state corresponds to the boson peak observed in light and neutron scattering spectra of glass-formers. The frequency of the boson peak is not dependent on the length scale of polar∕non-polar heterogeneity of ionic liquids, it depends instead on the strength of anion-cation interaction. As long as the boson peak is assigned to a mixing between localized modes and transverse acoustic excitations of high wavevectors, it is proposed that the other component observed in Raman spectra of ionic liquids has a partial character of longitudinal acoustic excitations. PMID:23514505

  10. Charge trapping in imidazolium ionic liquids.

    PubMed

    Shkrob, Ilya A; Wishart, James F

    2009-04-23

    Room-temperature ionic liquids (ILs) are a promising class of solvents for applications ranging from photovoltaics to solvent extractions. Some of these applications involve the exposure of the ILs to ionizing radiation, which stimulates interest in their radiation and photo- chemistry. In the case of ILs consisting of 1,3-dialkylimidazolium cations and hydrophobic anions, ionization, charge transfer and redox reactions yield charge-trapped species thought to be radicals resulting from neutralization of the constituent ions. Using computational chemistry methods and the recent results on electron spin resonance (ESR) and transient absorption spectroscopy of the ionized ILs, we argue that electron localization in the imidazolium ILs yields a gauche dimer radical cation with the elongated C(2)-C(2) bond. This species is shown to absorb in the near-infrared and the visible regions and accounts for the observed ESR spectra. We suggest that the excess electron in these aromatic ILs is localized as such a dimeric ion, and consider the chemical implications of this attribution. We also suggest that three-electron N-N bonding with the formation of a dimer radical anion occurs for amide anions, such as dicyanamide, when the parent anion traps holes; steric hindrance prevents the analogous reaction for bis(triflyl)amide anion. For another anion of practical importance, bis(oxalato)borate, a pathway involving the elimination of CO(2) is suggested. Together, these results indicate the unanticipated tendency of the ILs to localize primary charges as radical ions as opposed to neutral radicals. Thus, it appears that secondary chemistry in the ionized ILs may be dominated by radical ion reactions, similarly to the previously studied conventional organic liquids, depending on the composition of the IL. PMID:19323543

  11. Application of Ionic Liquids in Hydrometallurgy

    PubMed Central

    Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

    2014-01-01

    Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

  12. Application of ionic liquids in hydrometallurgy.

    PubMed

    Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

    2014-01-01

    Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

  13. Radiation Chemistry and Photochemistry of Ionic Liquids

    SciTech Connect

    Wishart, J.F.; Takahaski, K.

    2010-12-01

    As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

  14. Thermoelectric Potential of Polymer-Scaffolded Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Datta, R. S.; Said, S. M.; Sahamir, S. R.; Karim, M. R.; Sabri, M. F. M.; Nakajo, T.; Kubouchi, M.; Hayashi, K.; Miyazaki, Y.

    2014-06-01

    Organic thin films have been viewed as potential thermoelectric (TE) materials, given their ease of fabrication, flexibility, cost effectiveness, and low thermal conductivity. However, their intrinsically low electrical conductivity is a main drawback which results in a relatively lower TE figure of merit for polymer-based TE materials than for inorganic materials. In this paper, a technique to enhance the ion transport properties of polymers through the introduction of ionic liquids is presented. The polymer is in the form of a nanofiber scaffold produced using the electrospinning technique. These fibers were then soaked in different ionic liquids based on substituted imidazolium such as 1-ethyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium bromide. This method was applied to electrospun polyacrylonitrile and a mixture of polyvinyl alcohol and chitosan polymers. The ion transport properties of the membranes have been observed to increase with increasing concentration of ionic liquid, with maximum electrical conductivity of 1.20 × 10-1 S/cm measured at room temperature. Interestingly, the maximum electrical conductivity value surpassed the value of pure ionic liquids. These results indicate that it is possible to significantly improve the electrical conductivity of a polymer membrane through a simple and cost-effective method. This may in turn boost the TE figures of merit of polymer materials, which are well known to be considerably lower than those of inorganic materials. Results in terms of the Seebeck coefficient of the membranes are also presented in this paper to provide an overall representation of the TE potential of the polymer-scaffolded ionic liquid membranes.

  15. A Na(+) Superionic Conductor for Room-Temperature Sodium Batteries.

    PubMed

    Song, Shufeng; Duong, Hai M; Korsunsky, Alexander M; Hu, Ning; Lu, Li

    2016-01-01

    Rechargeable lithium ion batteries have ruled the consumer electronics market for the past 20 years and have great significance in the growing number of electric vehicles and stationary energy storage applications. However, in addition to concerns about electrochemical performance, the limited availability of lithium is gradually becoming an important issue for further continued use and development of lithium ion batteries. Therefore, a significant shift in attention has been taking place towards new types of rechargeable batteries such as sodium-based systems that have low cost. Another important aspect of sodium battery is its potential compatibility with the all-solid-state design where solid electrolyte is used to replace liquid one, leading to simple battery design, long life span, and excellent safety. The key to the success of all-solid-state battery design is the challenge of finding solid electrolytes possessing acceptable high ionic conductivities at room temperature. Herein, we report a novel sodium superionic conductor with NASICON structure, Na3.1Zr1.95Mg0.05Si2PO12 that shows high room-temperature ionic conductivity of 3.5 × 10(-3) S cm(-1). We also report successful fabrication of a room-temperature solid-state Na-S cell using this conductor. PMID:27572915

  16. A Na+ Superionic Conductor for Room-Temperature Sodium Batteries

    PubMed Central

    Song, Shufeng; Duong, Hai M.; Korsunsky, Alexander M.; Hu, Ning; Lu, Li

    2016-01-01

    Rechargeable lithium ion batteries have ruled the consumer electronics market for the past 20 years and have great significance in the growing number of electric vehicles and stationary energy storage applications. However, in addition to concerns about electrochemical performance, the limited availability of lithium is gradually becoming an important issue for further continued use and development of lithium ion batteries. Therefore, a significant shift in attention has been taking place towards new types of rechargeable batteries such as sodium-based systems that have low cost. Another important aspect of sodium battery is its potential compatibility with the all-solid-state design where solid electrolyte is used to replace liquid one, leading to simple battery design, long life span, and excellent safety. The key to the success of all-solid-state battery design is the challenge of finding solid electrolytes possessing acceptable high ionic conductivities at room temperature. Herein, we report a novel sodium superionic conductor with NASICON structure, Na3.1Zr1.95Mg0.05Si2PO12 that shows high room-temperature ionic conductivity of 3.5 × 10−3 S cm−1. We also report successful fabrication of a room-temperature solid-state Na-S cell using this conductor. PMID:27572915

  17. Ionic liquid enabled FeS2 for high-energy-density lithium-ion batteries.

    PubMed

    Evans, Tyler; Piper, Daniela Molina; Kim, Seul Cham; Han, Sang Sub; Bhat, Vinay; Oh, Kyu Hwan; Lee, Se-Hee

    2014-11-19

    High-energy-density FeS2 cathodes en-abled by a bis(trifluoromethanesulfonyl)imide (TFSI-) anion-based room temperature ionic liquid (RTIL) electrolyte are demonstrated. A TFSI-based ionic liquid (IL) significantly mitigates polysulfide dissolution, and therefore the parasitic redox shuttle mechanism, that plagues sulfur-based electrode chemistries. FeS2 stabilization with a TFSI(-) -based IL results in one of the highest energy density cathodes, 542 W h kg(-1) (normalized to cathode composite mass), reported to date. PMID:25236752

  18. Ultrafast diffusion of Ionic Liquids Confined in Carbon Nanotubes.

    PubMed

    Ghoufi, Aziz; Szymczyk, Anthony; Malfreyt, Patrice

    2016-01-01

    Over the past decade many works have focused on various aspects of the dynamics of liquids confined at the nanoscale such as e.g. water flow enhancement through carbon nanotubes (CNTs). Transport of room temperature ionic liquids (RTILs) through various nanochannels has also been explored and some conflicting findings about their translational dynamics have been reported. In this work, we focus on translational dynamics of RTILs confined in various CNTs. By means of molecular dynamics simulations we highlight a substantially enhanced diffusion of confined RTILs with an increase up to two orders of magnitude with respect to bulk-phase properties. This ultrafast diffusion of RTILs inside CNTs is shown to result from the combination of various factors such as low friction, molecular stacking, size, helicity, curvature and cooperative dynamics effects. PMID:27334208

  19. Ultrafast diffusion of Ionic Liquids Confined in Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Ghoufi, Aziz; Szymczyk, Anthony; Malfreyt, Patrice

    2016-06-01

    Over the past decade many works have focused on various aspects of the dynamics of liquids confined at the nanoscale such as e.g. water flow enhancement through carbon nanotubes (CNTs). Transport of room temperature ionic liquids (RTILs) through various nanochannels has also been explored and some conflicting findings about their translational dynamics have been reported. In this work, we focus on translational dynamics of RTILs confined in various CNTs. By means of molecular dynamics simulations we highlight a substantially enhanced diffusion of confined RTILs with an increase up to two orders of magnitude with respect to bulk-phase properties. This ultrafast diffusion of RTILs inside CNTs is shown to result from the combination of various factors such as low friction, molecular stacking, size, helicity, curvature and cooperative dynamics effects.

  20. Ultrafast diffusion of Ionic Liquids Confined in Carbon Nanotubes

    PubMed Central

    Ghoufi, Aziz; Szymczyk, Anthony; Malfreyt, Patrice

    2016-01-01

    Over the past decade many works have focused on various aspects of the dynamics of liquids confined at the nanoscale such as e.g. water flow enhancement through carbon nanotubes (CNTs). Transport of room temperature ionic liquids (RTILs) through various nanochannels has also been explored and some conflicting findings about their translational dynamics have been reported. In this work, we focus on translational dynamics of RTILs confined in various CNTs. By means of molecular dynamics simulations we highlight a substantially enhanced diffusion of confined RTILs with an increase up to two orders of magnitude with respect to bulk-phase properties. This ultrafast diffusion of RTILs inside CNTs is shown to result from the combination of various factors such as low friction, molecular stacking, size, helicity, curvature and cooperative dynamics effects. PMID:27334208

  1. A roadmap to uranium ionic liquids: anti-crystal engineering.

    PubMed

    Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

    2014-05-19

    In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. PMID:24737451

  2. A roadmap to uranium ionic liquids: Anti-crystal engineering

    DOE PAGESBeta

    Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja -Verena

    2014-04-15

    In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO22+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim tomore » establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.« less

  3. A roadmap to uranium ionic liquids: Anti-crystal engineering

    SciTech Connect

    Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja -Verena

    2014-04-15

    In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO22+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.

  4. Enzyme catalysis with small ionic liquid quantities.

    PubMed

    Fischer, Fabian; Mutschler, Julien; Zufferey, Daniel

    2011-04-01

    Enzyme catalysis with minimal ionic liquid quantities improves reaction rates, stereoselectivity and enables solvent-free processing. In particular the widely used lipases combine well with many ionic liquids. Demonstrated applications are racemate separation, esterification and glycerolysis. Minimal solvent processing is also an alternative to sluggish solvent-free catalysis. The method allows simplified down-stream processing, as only traces of ionic liquids have to be removed. PMID:21107639

  5. Early Events in Ionic Liquid Radiation Chemistry

    SciTech Connect

    Wishart, J.F.; Cook, A.; Rimmer, R.D.; Gohdo, M.

    2010-09-14

    Ionic liquids are interesting and useful materials whose solvation time scales are up to thousands of times longer than in conventional solvents. The extended lifetimes of pre-solvated electrons and other energetic species in ionic liquids has profound consequences for the radiolytic product distributions and reactivity patterns. We use a newly developed, multiplexed variation of pulse-probe spectroscopy to measure the kinetics of the early dynamical and reactive events in ionic liquids.

  6. Preparation and characterisation of high-density ionic liquids incorporating halobismuthate anions.

    PubMed

    Cousens, Nico E A; Taylor Kearney, Leah J; Clough, Matthew T; Lovelock, Kevin R J; Palgrave, Robert G; Perkin, Susan

    2014-07-28

    A range of ionic liquids containing dialkylimidazolium cations and halobismuthate anions ([BiBr(x)Cl(y)I(z)](-) and [Bi2Br(x)Cl(y)I(z)](-)) were synthesised by combining dialkylimidazolium halide ionic liquids with bismuth(III) halide salts. The majority were room temperature liquids, all with very high densities. The neat ionic liquids and their mixtures with 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide were characterised using Densitometry, Viscometry, NMR Spectroscopy, Electrospray Ionisation Mass Spectrometry (ESI), Liquid Secondary Ion Mass Spectrometry (LSIMS), Matrix-assisted Laser Desorption/Ionization Mass Spectrometry (MALDI), X-Ray Photoelectron Spectroscopy (XPS) and Thermogravimetric Analysis (TGA), to establish their speciation and suitability for high-temperature applications. PMID:24898158

  7. Vertical alignment of liquid crystal through ion beam exposure on oxygen-doped SiC films deposited at room temperature

    SciTech Connect

    Son, Phil Kook; Park, Jeung Hun; Kim, Jae Chang; Yoon, Tae-Hoon; Rho, Soon Joon; Jeon, Back Kyun; Shin, Sung Tae; Kim, Jang Sub; Lim, Soon Kwon

    2007-09-03

    The authors report the vertical alignment of liquid crystal (LC) through the ion beam exposure on amorphous oxygen-doped SiC (SiOC) film surfaces deposited at room temperature. The optical transmittance of these films was similar to that of polyimide layers, but much higher than that of SiO{sub x} films. The light leakage of a LC cell aligned vertically on SiOC films was much lower than those of a LC cell aligned on polyimide layers or other inorganic films. They found that LC molecules align vertically on ion beam treated SiOC film when the roughness of the electrostatic force microscopy (EFM) data is high on the SiOC film surface, while they align homogeneously when the roughness of the EFM data is low.

  8. Ion field-evaporation from ionic liquids infusing carbon xerogel microtips

    SciTech Connect

    Perez-Martinez, C. S. Lozano, P. C.

    2015-07-27

    Ionic liquid ion sources capable of producing positive and negative molecular ion beams from room-temperature molten salts have applications in diverse fields, from materials science to space propulsion. The electrostatic stressing of these ionic liquids places the liquid surfaces in a delicate balance that could yield unwanted droplet emission when not properly controlled. Micro-tip emitter configurations are required to guarantee that these sources will operate in a pure ionic regime with no additional droplets. Porous carbon based on resorcinol-formaldehyde xerogels is introduced as an emitter substrate. It is demonstrated that this material can be shaped to the required micron-sized geometry and has appropriate transport properties to favor pure ionic emission. Time-of-flight mass spectrometry is used to verify that charged particle beams contain solvated ions exclusively.

  9. Ion field-evaporation from ionic liquids infusing carbon xerogel microtips

    NASA Astrophysics Data System (ADS)

    Perez-Martinez, C. S.; Lozano, P. C.

    2015-07-01

    Ionic liquid ion sources capable of producing positive and negative molecular ion beams from room-temperature molten salts have applications in diverse fields, from materials science to space propulsion. The electrostatic stressing of these ionic liquids places the liquid surfaces in a delicate balance that could yield unwanted droplet emission when not properly controlled. Micro-tip emitter configurations are required to guarantee that these sources will operate in a pure ionic regime with no additional droplets. Porous carbon based on resorcinol-formaldehyde xerogels is introduced as an emitter substrate. It is demonstrated that this material can be shaped to the required micron-sized geometry and has appropriate transport properties to favor pure ionic emission. Time-of-flight mass spectrometry is used to verify that charged particle beams contain solvated ions exclusively.

  10. Partition coefficients of organic compounds between water and imidazolium-, pyridinium-, and phosphonium-based ionic liquids.

    PubMed

    Padró, Juan M; Pellegrino Vidal, Rocío B; Reta, Mario

    2014-12-01

    The partition coefficients, P IL/w, of several compounds, some of them of biological and pharmacological interest, between water and room-temperature ionic liquids based on the imidazolium, pyridinium, and phosphonium cations, namely 1-octyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium tetrafluorophosphate, trihexyl(tetradecyl)phosphonium chloride, trihexyl(tetradecyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium dicyanamide, were accurately measured. In this way, we extended our database of partition coefficients in room-temperature ionic liquids previously reported. We employed the solvation parameter model with different probe molecules (the training set) to elucidate the chemical interactions involved in the partition process and discussed the most relevant differences among the three types of ionic liquids. The multiparametric equations obtained with the aforementioned model were used to predict the partition coefficients for compounds (the test set) not present in the training set, most being of biological and pharmacological interest. An excellent agreement between calculated and experimental log P IL/w values was obtained. Thus, the obtained equations can be used to predict, a priori, the extraction efficiency for any compound using these ionic liquids as extraction solvents in liquid-liquid extractions. PMID:25326892

  11. Membrane separation of ionic liquid solutions

    SciTech Connect

    Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

    2015-09-01

    A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

  12. Charge transport in confined ionic liquids

    NASA Astrophysics Data System (ADS)

    Sangoro, Joshua; Iacob, Ciprian; Kipnusu, Wycliffe; Kremer, Friedrich

    2011-03-01

    Charge transport and glassy dynamics in neat and polymerized ionic liquids confined in nanoporous silica are investigated in a wide frequency and temperature ranges by a combination of Broadband Dielectric Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). By applying the Einstein-Smoluchowski relations to the dielectric spectra, diffusion coefficients are obtained in quantitative agreement with independent PFG NMR. The impact of geometrical confinement as well as the pore wall-ionic liquid interactions on the overall ionic mobility is explored for diverse categories of ionic liquids. The results are discussed within the framework of dynamic glass transition assisted charge transport in ionic liquids. Financial support from the Deutsche Forschungsgemeinschaft under the DFG SPP 1191 Priority Program on Ionic Liquids is gratefully acknowledged.

  13. Ionic liquids screening for desulfurization of natural gasoline by liquid-liquid extraction.

    PubMed

    Likhanova, Natalya V; Guzmán-Lucero, Diego; Flores, Eugenio A; García, Paloma; Domínguez-Aguilar, Marco A; Palomeque, Jorge; Martínez-Palou, Rafael

    2010-11-01

    Seventy five ionic liquids (ILs) were tested as a sequestering agent of sulfured compounds in natural gasoline (NG). Desulphurization of NG was performed by means of liquid-liquid extraction method at room temperature and atmospheric pressure. Experimental ILs containing imidazolium, pyridinium, and ammonium cations along with organic and inorganic anions were synthesized conventionally and under microwave and sonochemical conditions. The effect of the molecular structure of ILs on the desulfurization efficiency of NG with high sulfur content was evaluated. Analysis indicated that the anion type played a more important role than the cation on the desulphurization process. ILs based on halogen-ferrates and halogen-aluminates exhibited the highest efficiency in sulfur removal, and their efficiency is further improved when there is an excess of metallic salt in a ratio of at least 1:1.3 during the synthesis of the corresponding IL. An explanation for the ability of metallic ILs to remove sulfur-containing compounds from natural gasoline based on the ratio of the ionic charge to the atomic radius is proposed. Furthermore, a method to recover and reuse water-sensitive to halogenated precursors is described. PMID:20091120

  14. Ionic liquid tunes microemulsion curvature.

    PubMed

    Liu, Liping; Bauduin, Pierre; Zemb, Thomas; Eastoe, Julian; Hao, Jingcheng

    2009-02-17

    Middle-phase microemulsions formed from cationic dioctadecyldimethylammonium chloride (DODMAC), anionic sodium dodecylsulfate (SDS), n-butanol, and n-heptane were studied. An ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), was employed as the electrolyte in the aqueous media instead of inorganic salts usually used in microemulsion formulation. Studies have been carried out as a function of the concentrations of [bmim][BF4], n-butanol, total surfactant (cDODMAC+SDS), and temperature on the phase behavior and the ultralow interfacial tensions in which the anionic component is present in excess in the catanionic film. Ultralow interfacial tension measurements confirmed the formation of middle-phase microemulsions and the necessary conditions for stabilizing middle-phase microemulsions. Electrical conductivity, small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) experiments were also performed, indicating that the typical heptane domain size has an average radius of 360 A and the ionic liquid induces softening of the charged catanionic film. Most interestingly, the IL concentration (cIL) is shown to act as an effective interfacial curvature-control parameter, representing a new approach to tuning the formulation of microemulsions and emulsions. The results expand the potential uses of ILs but also point to the design of new ILs that may achieve superefficient control over interfacial and self-assembly systems. PMID:19161325

  15. Metathesis of Fatty Acid Ester Derivatives in 1,1-Dialkyl and 1,2,3-Trialkyl Imidazolium Type Ionic Liquids

    PubMed Central

    Thomas, Priya A.; Marvey, Bassie B.; Ebenso, Eno E.

    2011-01-01

    The self-metathesis of methyl oleate and methyl ricinoleate was carried out in the presence of ruthenium alkylidene catalysts 1–4 in [bmim] and [bdmim][X] type ionic liquids (RTILs) (X = PF6−, BF4− and NTf2−) using the gas chromatographic technique. Best catalytic performance was obtained in [bdmim][X] type ionic liquids when compared with [bmim][X] type ionic liquids. Catalyst recycling studies were also carried out in the room temperature ionic liquids (RTILs) with catalysts 1–4 in order to explore their possible industrial application. PMID:21747719

  16. Novel polymer electrolytes based on gelatin and ionic liquids

    NASA Astrophysics Data System (ADS)

    Leones, Rita; Sentanin, F.; Rodrigues, Luísa C.; Ferreira, Rute A. S.; Marrucho, Isabel M.; Esperança, José M. S. S.; Pawlicka, Agnieszka; Carlos, Luís D.; Manuela Silva, M.

    2012-12-01

    This study describes the results of the characterization of polymer electrolytes using gelatin matrix doped with europium triflate and/or different ionic liquids. Samples of solvent-free electrolytes were prepared and characterized by ionic conductivity measurements, thermal analysis, electrochemical stability, X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. Electrolyte samples are thermally stable up to approximately 220 °C. All the materials synthesized are totally amorphous. The room temperature conductivity maximum of this electrolyte system is based on ionic liquid 1-ethyl-3-methylimidazolium acetate, (C2mim)(OAc) (1.18 × 10-4 S cm-1 at 30 °C). The electrochemical stability domain of all samples is about 2.0 V versus Li/Li+. This new series of materials represents a promising alternative in polymer electrolytes research field. The preliminary studies carried out with electrochromic devices (ECDs) incorporating optimized compositions have confirmed that these materials may perform as satisfactory multifunctional component layers in the field of "smart windows". This new materials, will open a land of promising applications in many areas: optics, energy, medicine for example as membranes and separation devices, ECD-based devices, sensors, etc.

  17. Effect of Embedded Pd Microstructures on the Flat-Band-Voltage Operation of Room Temperature ZnO-Based Liquid Petroleum Gas Sensors

    PubMed Central

    Ali, Ghusoon M.; Thompson, Cody V.; Jasim, Ali K.; Abdulbaqi, Isam M.; Moore, James C.

    2013-01-01

    Three methods were used to fabricate ZnO-based room temperature liquid petroleum gas (LPG) sensors having interdigitated metal-semiconductor-metal (MSM) structures. Specifically, devices with Pd Schottky contacts were fabricated with: (1) un-doped ZnO active layers; (2) Pd-doped ZnO active layers; and (3) un-doped ZnO layers on top of Pd microstructure arrays. All ZnO films were grown on p-type Si(111) substrates by the sol-gel method. For devices incorporating a microstructure array, Pd islands were first grown on the substrate by thermal evaporation using a 100 μm mesh shadow mask. We have estimated the sensitivity of the sensors for applied voltage from –5 to 5 V in air ambient, as well as with exposure to LPG in concentrations from 500 to 3,500 ppm at room temperature (300 K). The current-voltage characteristics were studied and parameters such as leakage current, barrier height, reach-through voltage, and flat-band voltage were extracted. We include contributions due to the barrier height dependence on the electric field and tunneling through the barrier for the studied MSM devices. The Pd-enhanced devices demonstrated a maximum gas response at flat-band voltages. The study also revealed that active layers consisting of Pd microstructure embedded ZnO films resulted in devices exhibiting greater gas-response as compared to those using Pd-doped ZnO thin films or un-doped active layers.

  18. Quantized friction across ionic liquid thin films.

    PubMed

    Smith, Alexander M; Lovelock, Kevin R J; Gosvami, Nitya Nand; Welton, Tom; Perkin, Susan

    2013-10-01

    Ionic liquids - salts in the liquid state under ambient conditions - are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition. PMID:23942943

  19. Liquid metal alloy ion source based metal ion injection into a room-temperature electron beam ion source

    SciTech Connect

    Thorn, A.; Ritter, E.; Zschornack, G.; Ullmann, F.; Pilz, W.; Bischoff, L.

    2012-02-15

    We have carried out a series of measurements demonstrating the feasibility of using the Dresden electron beam ion source (EBIS)-A, a table-top sized, permanent magnet technology based electron beam ion source, as a charge breeder. Low charged gold ions from an AuGe liquid metal alloy ion source were injected into the EBIS and re-extracted as highly charged ions, thereby producing charge states as high as Au{sup 60+}. The setup, the charge breeding technique, breeding efficiencies as well as acceptance and emittance studies are presented.

  20. Crosslinked polymer gel electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium battery applications

    SciTech Connect

    Liao, Chen; Sun, Xiao-Guang; Dai, Sheng

    2013-01-01

    Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g 1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g 1 by using a thinner membrane and cycling at 50 C.

  1. Ionic liquid-in-oil microemulsions.

    PubMed

    Eastoe, Julian; Gold, Sarah; Rogers, Sarah E; Paul, Alison; Welton, Tom; Heenan, Richard K; Grillo, Isabelle

    2005-05-25

    Phase stability and small-angle neutron scattering (SANS) data show that surfactant-stabilized nanodomains of a typical ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4]) may be dispersed by the nonionic surfactant Triton-X100 in cyclohexane. Analyses of these SANS data are consistent with the formation of ionic liquid-in-oil microemulsion droplets. PMID:15898765

  2. Engineered microorganisms having resistance to ionic liquids

    DOEpatents

    Ruegg, Thomas Lawrence; Thelen, Michael P.

    2016-03-22

    The present invention provides for a method of genetically modifying microorganisms to enhance resistance to ionic liquids, host cells genetically modified in accordance with the methods, and methods of using the host cells in a reaction comprising biomass that has been pretreated with ionic liquids.

  3. Protein Structure and Stability in Neat Ionic Liquid

    NASA Astrophysics Data System (ADS)

    Bihari, Malvika; Russell, Thomas P.; Hoagland, David A.

    2010-03-01

    Ionic liquid (IL) as a medium for room temperature preservation of biomacromolecules has been proposed, and to investigate the possibility, we studied physicochemical and enzymatic properties of several proteins in the neat hydrophilic IL, ethylmethyl imidazolium ethyl sulfate [EMIM][EtSO4]. Molecular dissolution of α-chymotypsin, cytochrome-c and other proteins could be achieved with moderate heating (60C). Dynamic light scattering and dilute solution viscometry typically reveal protein size slightly larger than in buffer, suggesting different solvation or protein unfolding. Spectroscopic methods (UV-Vis, fluorescence, FTIR, CD) show largely unchanged secondary structure but significantly changed tertiary structure. IL-dissolved cytochrome-c has heightened peroxidase activity, supporting the same conclusions. Transfer of dissolved protein from IL to buffer and ensuing alterations to protein conformation/activity will be discussed.

  4. Fluorescence correlation spectroscopy evidence for structural heterogeneity in ionic liquids

    SciTech Connect

    Guo, J C; Baker, G. A.; Hillesheim, P. C.; Dai, S.; Shaw, R. W.; Mahurin, S., M.

    2011-01-01

    In this work, we provide new experimental evidence for chain length-dependent self-aggregation in room temperature ionic liquids (RTILs) using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [C{sub n}MPy][Tf{sub 2}N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decreased with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chain [C{sub n}MPy][Tf{sub 2}N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [CnMPy]{sup +}.

  5. Ionic Liquids for the Imaging of Wet Polymer Morphology

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John; Bihari, Malvika

    2011-03-01

    Unlike convention aqueous and organic solvents, ionic liquids are essentially nonvolatile and thus compatible with the high vacuum environments of electron microscopy. Here is described the room temperature imaging of wet polymer systems such as patterned gels, gel networks, polymeric vesicles, and proteins. Both TEM and SEM images will be offered, along with a discussion of difficulties in applying the two techniques. Via SEM, imprinted surface structures as small as 100-300 nm can be captured for chemically crosslinked gels (polyHEMA), and via TEM, the structure of a physical gel (PEG) is viewed at the 50-to-10-nm scale, revealing network connectivity established by PEG crystallinity. Self-assembled vesicle and micelle structures will be presented for dispersed block copolymers, and the same approach will be applied toward discerning the quality of dispersion for proteins (ferritin) and other nanoparticles. Funding: UMass MRSEC.

  6. Protic ionic liquids with fluorous anions: physicochemical properties and self-assembly nanostructure.

    PubMed

    Shen, Yan; Kennedy, Danielle F; Greaves, Tamar L; Weerawardena, Asoka; Mulder, Roger J; Kirby, Nigel; Song, Gonghua; Drummond, Calum J

    2012-06-14

    A series of 11 new protic ionic liquids with fluorous anions (FPILs) have been identified and their self-assembled nanostructure, thermal phase transitions and physicochemical properties were investigated. To the best of our knowledge this is the first time that fluorocarbon domains have been reported in PILs. The FPILs were prepared from a range of hydrocarbon alkyl and heterocyclic amine cations in combination with the perfluorinated anions heptafluorobutyrate and pentadecafluorooctanoate. The nanostructure of the FPILs was established by using small- and wide-angle X-ray scattering (SAXS and WAXS). In the liquid state many of the FPILs showed an intermediate range order, or self-assembled nanostructure, resulting from segregation of the polar and nonpolar hydrocarbon and fluorocarbon domains of the ionic liquid. In addition, the physicochemical properties of the FPILs were determined including the melting point (T(m)), glass transition (T(g)), devitrification temperature (T(c)), thermal stability and the density ρ, viscosity η, air/liquid surface tension γ(LV), refractive index n(D), and ionic conductivity κ. The FPILs were mostly solids at room temperature, however two examples 2-pyrrolidinonium heptafluorobutyrate (PyrroBF) and pyrrolidinium heptafluorobutyrate (PyrrBF) were liquids at room temperature and all of the FPILs melted below 80 °C. Four of the FPILs exhibited a glass transition. The two liquids at room temperature, PyrroBF and PyrrBF, had a similar density, surface tension and refractive index but their viscosity and ionic conductivity were very different due to dissimilar self-assembled nanostructure. PMID:22569799

  7. Ionic liquid incorporating thiosalicylate for metal removal

    NASA Astrophysics Data System (ADS)

    Wilfred, Cecilia Devi; Mustafa, Fadwa Babiker; Romeli, Fatimah Julia

    2012-09-01

    Ionic liquids are a class of organic molten salts "designer solvents" that are composed totally of anions (inorganic and organic polyatomic) and organic cations. The replacement of volatile organic solvents from a separation process is of utmost importance since the use of a large excess of these solvents is hazardous and creates ecological problem. The new method for metal ion extraction is by using task-specific ionic liquids such as ionic liquids which incorporate thiosalicylate functionality. This paper looks at producing a new cluster of ionic liquids which incorporates thiosalicylate with pyridinium cation. Its thermophysical properties such as density and viscosity in single and binary mixtures are studied. The ionic liquids' capability in metal removal processes is evaluated.

  8. Ion gels by self-assembly of a triblock copolymer in an ionic liquid.

    PubMed

    He, Yiyong; Boswell, Paul G; Bühlmann, Philippe; Lodge, Timothy P

    2007-05-10

    We report a new way of developing ion gels through the self-assembly of a triblock copolymer in a room-temperature ionic liquid. Transparent ion gels were achieved by gelation of a poly(styrene-block-ethylene oxide-block-styrene) (SOS) triblock copolymer in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) with as low as 5 wt % SOS triblock copolymer. The gelation behavior, ionic conductivity, rheological properties, and microstructure of the ion gels were investigated. The ionic conductivity of the ion gels is only modestly affected by the triblock copolymer network. Its temperature dependence nearly tracks that of the bulk ionic liquid viscosity. The ion gels are thermally stable up to at least 100 degrees C and possess significant mechanical strength. The results presented here suggest that triblock copolymer gelation is a promising way to develop highly conductive ion gels and provides many advantages in terms of variety and processing. PMID:17474692

  9. Liquid crystal self-assembly of halloysite nanotubes in ionic liquids: a novel soft nanocomposite ionogel electrolyte with high anisotropic ionic conductivity and thermal stability

    NASA Astrophysics Data System (ADS)

    Zhao, Ningning; Liu, Yulin; Zhao, Xiaomeng; Song, Hongzan

    2016-01-01

    We report a novel class of liquid crystalline (LC) nanohybrid ionogels fabricated via self-assembly of natural halloysite nanotubes (HNTs) in ionic liquids (ILs). The obtained ionogels are very stable and nonvolatile and show LC phases over a wide temperature range. Remarkably, the nanocomposite ionogels exhibit high anisotropic ionic conductivity after shear, and their room temperature ionic conductivity can reach 3.8 × 10-3 S cm-1 for aligned nanotubes perpendicular to the electrode even when the HNTs content increases to 40 wt%, which is 380 times higher than that obtained for aligned nanotubes parallel to the electrode, which is 1.0 × 10-5 S cm-1. Crucially, the obtained LC nanocomposite ionogels have very high thermal stability, which can sustain 400 °C thermal treatment. The findings will promote the development of novel nanocomposite ionogel electrolytes with faster ion transport and larger anisotropic conductivity.We report a novel class of liquid crystalline (LC) nanohybrid ionogels fabricated via self-assembly of natural halloysite nanotubes (HNTs) in ionic liquids (ILs). The obtained ionogels are very stable and nonvolatile and show LC phases over a wide temperature range. Remarkably, the nanocomposite ionogels exhibit high anisotropic ionic conductivity after shear, and their room temperature ionic conductivity can reach 3.8 × 10-3 S cm-1 for aligned nanotubes perpendicular to the electrode even when the HNTs content increases to 40 wt%, which is 380 times higher than that obtained for aligned nanotubes parallel to the electrode, which is 1.0 × 10-5 S cm-1. Crucially, the obtained LC nanocomposite ionogels have very high thermal stability, which can sustain 400 °C thermal treatment. The findings will promote the development of novel nanocomposite ionogel electrolytes with faster ion transport and larger anisotropic conductivity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06888f

  10. Recent advances in the use of ionic liquids for electrochemical sensing.

    PubMed

    Silvester, Debbie S

    2011-12-01

    Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented. PMID:22013585

  11. Fast Ignition and Sustained Combustion of Ionic Liquids

    NASA Technical Reports Server (NTRS)

    Joshi, Prakash B. (Inventor); Piper, Lawrence G. (Inventor); Oakes, David B. (Inventor); Sabourin, Justin L. (Inventor); Hicks, Adam J. (Inventor); Green, B. David (Inventor); Tsinberg, Anait (Inventor); Dokhan, Allan (Inventor)

    2016-01-01

    A catalyst free method of igniting an ionic liquid is provided. The method can include mixing a liquid hypergol with a HAN (Hydroxylammonium nitrate)-based ionic liquid to ignite the HAN-based ionic liquid in the absence of a catalyst. The HAN-based ionic liquid and the liquid hypergol can be injected into a combustion chamber. The HAN-based ionic liquid and the liquid hypergol can impinge upon a stagnation plate positioned at top portion of the combustion chamber.

  12. Actinide chemistry in ionic liquids.

    PubMed

    Takao, Koichiro; Bell, Thomas James; Ikeda, Yasuhisa

    2013-04-01

    This Forum Article provides an overview of the reported studies on the actinide chemistry in ionic liquids (ILs) with a particular focus on several fundamental chemical aspects: (i) complex formation, (ii) electrochemistry, and (iii) extraction behavior. The majority of investigations have been dedicated to uranium, especially for the 6+ oxidation state (UO2(2+)), because the chemistry of uranium in ordinary solvents has been well investigated and uranium is the most abundant element in the actual nuclear fuel cycles. Other actinides such as thorium, neptunium, plutonium, americium, and curiumm, although less studied, are also of importance in fully understanding the nuclear fuel engineering process and the safe geological disposal of radioactive wastes. PMID:22873132

  13. Lipid Biomembrane in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Yoo, Brian; Jing, Benxin; Shah, Jindal; Maginn, Ed; Zhu, Y. Elaine; Department of Chemical and Biomolecular Engineering Team

    2014-03-01

    Ionic liquids (ILs) have been recently explored as new ``green'' chemicals in several chemical and biomedical processes. In our pursuit of understanding their toxicities towards aquatic and terrestrial organisms, we have examined the IL interaction with lipid bilayers as model cell membranes. Experimentally by fluorescence microscopy, we have directly observed the disruption of lipid bilayer by added ILs. Depending on the concentration, alkyl chain length, and anion hydrophobicity of ILs, the interaction of ILs with lipid bilayers leads to the formation of micelles, fibrils, and multi-lamellar vesicles for IL-lipid complexes. By MD computer simulations, we have confirmed the insertion of ILs into lipid bilayers to modify the spatial organization of lipids in the membrane. The combined experimental and simulation results correlate well with the bioassay results of IL-induced suppression in bacteria growth, thereby suggesting a possible mechanism behind the IL toxicity. National Science Foundation, Center for Research Computing at Notre Dame.

  14. Pentadecyl phenol- and cardanol-functionalized fluorescent, room-temperature liquid-crystalline perylene bisimides: effect of pendant chain unsaturation on self-assembly.

    PubMed

    Bhavsar, Ghanashyam A; Asha, S K

    2011-11-01

    A new perylene bisimide (PBI) building block based on pentadecyl phenol (PDP) or cardanol was developed, which upon esterification with 3,4,5-tridodecyloxy gallate resulted in highly emissive, room-temperature liquid-crystalline (LC) molecules. The self assembly in solution was studied in detail by NMR spectroscopy, UV/Vis absorption, and fluorescence spectroscopy. In solution both PDP- and cardanol-based PBI exhibited similar behavior. They were molecularly dissolved in chloroform (CHCl(3)) but formed rotationally displaced H-type aggregates that emitted at 640 nm in methylcyclohexane (MCH). Surface morphology in dropcast films were characterized using microscopic techniques such as SEM, TEM, and atomic force microscopy (AFM). The liquid-crystalline properties were studied using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and variable-temperature X-ray (small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WXRD)) studies. Variable-temperature X-ray studies in the LC phase indicated strong π-π stacking interaction present in the PDP-based PBI derivative, whereas the stacking was absent in the LC phase of the cardanol-based PBI. The latter formed self-organized structures of extremely short length due to the presence of cis double bonds in the C15 alkyl side chain, whereas the saturated alkyl side chain in PDP could pack efficiently, thereby resulting in nanofibers that were several micrometers in length. PMID:21956257

  15. Electrochemical transistors with ionic liquids for enzymatic sensing

    NASA Astrophysics Data System (ADS)

    Fraser, Kevin J.; Yang, Sang Yoon; Cicoira, Fabio; Curto, Vincenzo F.; Byrne, Robert; Benito-Lopez, Fernando; Khodagholy, Dion; Owens, Róisín M.; Malliaras, George G.; Diamond, Dermot

    2011-10-01

    Over the past decade conducting polymer electrodes have played an important role in bio-sensing and actuation. Recent developments in the field of organic electronics have made available a variety of devices that bring unique capabilities at the interface with biology. One example is organic electrochemical transistors (OECTs) that are being developed for a variety of bio-sensing applications, including the detection of ions, and metabolites, such as glucose and lactate. Room temperature ionic liquids (RTILs) are organic salts, which are liquid at ambient temperature. Their nonvolatile character and thermal stability makes them an attractive alternative to conventional organic solvents. Here we report an enzymatic sensor based on an organic electro-chemical transistor with RTIL's as an integral part of its structure and as an immobilization medium for the enzyme and the mediator. Further investigation shows that these platforms can be incorporated into flexible materials such as carbon cloth and can be utilized for bio-sensing. The aim is to incorporate the overall platform in a wearable sensor to improve athlete performance with regards to training. In this manuscript an introduction to ionic liquids (ILs), IL - enzyme mixtures and a combination of these novel materials being used on OECTs are presented.

  16. Probing the interaction of ionic liquids with graphene using surface-enhanced Raman spectroscopy

    SciTech Connect

    Mahurin, Shannon Mark; Dai, Sheng; Surwade, Sumedh P.; Crespo, Marcos

    2015-12-17

    We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra of the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.

  17. Probing the interaction of ionic liquids with graphene using surface-enhanced Raman spectroscopy

    DOE PAGESBeta

    Mahurin, Shannon Mark; Dai, Sheng; Surwade, Sumedh P.; Crespo, Marcos

    2015-12-17

    We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra ofmore » the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.« less

  18. Polymer--Ionic liquid Electrolytes for Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Ketabi, Sanaz

    dielectric constant characteristic of the fillers contributed to the increased conductivity and cell capacitance. Leveraging the fillers, the ionic conductivity of the environmentally friendly polymer-ILs approached the level of the polymer-fluorinated IL at room temperature, and exceeded the latter at high temperature. Another approach to improve the performance of polymer electrolytes was undertaken through the development of protic ILs (PILs) and polymer-PIL electrolytes for pseudocapacitors. Binary eutectic systems of PILs were investigated, and the proton conduction of the eutectic systems was characterized in both liquid and polymer states. Devices enabled by PEO-EMIHSO4 and PEO-binary PILs demonstrated a comparable energy density to that with polymer-fluorinated ILs.

  19. Is the boundary layer of an ionic liquid equally lubricating at higher temperature?

    PubMed

    Hjalmarsson, Nicklas; Atkin, Rob; Rutland, Mark W

    2016-03-23

    Atomic force microscopy has been used to study the effect of temperature on normal forces and friction for the room temperature ionic liquid (IL) ethylammonium nitrate (EAN), confined between mica and a silica colloid probe at 25 °C, 50 °C, and 80 °C. Force curves revealed a strong fluid dynamic influence at room temperature, which was greatly reduced at elevated temperatures due to the reduced liquid viscosity. A fluid dynamic analysis reveals that bulk viscosity is manifested at large separation but that EAN displays a nonzero slip, indicating a region of different viscosity near the surface. At high temperatures, the reduction in fluid dynamic force reveals step-like force curves, similar to those found at room temperature using much lower scan rates. The ionic liquid boundary layer remains adsorbed to the solid surface even at high temperature, which provides a mechanism for lubrication when fluid dynamic lubrication is strongly reduced. The friction data reveals a decrease in absolute friction force with increasing temperature, which is associated with increased thermal motion and reduced viscosity of the near surface layers but, consistent with the normal force data, boundary layer lubrication was unaffected. The implications for ILs as lubricants are discussed in terms of the behaviour of this well characterised system. PMID:26976694

  20. Conductance modulation in topological insulator Bi{sub 2}Se{sub 3} thin films with ionic liquid gating

    SciTech Connect

    Son, Jaesung; Banerjee, Karan; Yang, Hyunsoo; Brahlek, Matthew; Koirala, Nikesh; Oh, Seongshik; Lee, Seoung-Ki; Ahn, Jong-Hyun

    2013-11-18

    A Bi{sub 2}Se{sub 3} topological insulator field effect transistor is investigated by using ionic liquid as an electric double layer gating material, leading to a conductance modulation of 365% at room temperature. We discuss the role of charged impurities on the transport properties. The conductance modulation with gate bias is due to a change in the carrier concentration, whereas the temperature dependent conductance change is originated from a change in mobility. Large conductance modulation at room temperature along with the transparent optical properties makes topological insulators as an interesting (opto)electronic material.

  1. Ionic liquids for rechargeable lithium batteries

    SciTech Connect

    Salminen, Justin; Papaiconomou, Nicolas; Kerr, John; Prausnitz,John; Newman, John

    2005-09-29

    We have investigated possible anticipated advantages of ionic-liquid electrolytes for use in lithium-ion batteries. Thermal stabilities and phase behavior were studied by thermal gravimetric analysis and differential scanning calorimetry. The ionic liquids studied include various imidazoliumTFSI systems, pyrrolidiniumTFSI, BMIMPF{sub 6}, BMIMBF{sub 4}, and BMIMTf. Thermal stabilities were measured for neat ionic liquids and for BMIMBF{sub 4}-LiBF{sub 4}, BMIMTf-LiTf, BMIMTFSI-LiTFSI mixtures. Conductivities have been measured for various ionic-liquid lithium-salt systems. We show the development of interfacial impedance in a Li|BMIMBF{sub 4} + LiBF{sub 4}|Li cell and we report results from cycling experiments for a Li|BMIMBF{sub 4} + 1 mol/kg LIBF{sub 4}|C cell. The interfacial resistance increases with time and the ionic liquid reacts with the lithium electrode. As expected, imidazolium-based ionic liquids react with lithium electrodes. We seek new ionic liquids that have better chemical stabilities.

  2. Carbon dioxide in an ionic liquid: Structural and rotational dynamics.

    PubMed

    Giammanco, Chiara H; Kramer, Patrick L; Yamada, Steven A; Nishida, Jun; Tamimi, Amr; Fayer, Michael D

    2016-03-14

    Ionic liquids (ILs), which have widely tunable structural motifs and intermolecular interactions with solutes, have been proposed as possible carbon capture media. To inform the choice of an optimal ionic liquid system, it can be useful to understand the details of dynamics and interactions on fundamental time scales (femtoseconds to picoseconds) of dissolved gases, particularly carbon dioxide (CO2), within the complex solvation structures present in these uniquely organized materials. The rotational and local structural fluctuation dynamics of CO2 in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2) were investigated by using ultrafast infrared spectroscopy to interrogate the CO2 asymmetric stretch. Polarization-selective pump probe measurements yielded the orientational correlation function of the CO2 vibrational transition dipole. It was found that reorientation of the carbon dioxide occurs on 3 time scales: 0.91 ± 0.03, 8.3 ± 0.1, 54 ± 1 ps. The initial two are attributed to restricted wobbling motions originating from a gating of CO2 motions by the IL cations and anions. The final (slowest) decay corresponds to complete orientational randomization. Two-dimensional infrared vibrational echo (2D IR) spectroscopy provided information on structural rearrangements, which cause spectral diffusion, through the time dependence of the 2D line shape. Analysis of the time-dependent 2D IR spectra yields the frequency-frequency correlation function (FFCF). Polarization-selective 2D IR experiments conducted on the CO2 asymmetric stretch in the parallel- and perpendicular-pumped geometries yield significantly different FFCFs due to a phenomenon known as reorientation-induced spectral diffusion (RISD), revealing strong vector interactions with the liquid structures that evolve slowly on the (independently measured) rotation time scales. To separate the RISD contribution to the FFCF from the structural spectral

  3. Carbon dioxide in an ionic liquid: Structural and rotational dynamics

    NASA Astrophysics Data System (ADS)

    Giammanco, Chiara H.; Kramer, Patrick L.; Yamada, Steven A.; Nishida, Jun; Tamimi, Amr; Fayer, Michael D.

    2016-03-01

    Ionic liquids (ILs), which have widely tunable structural motifs and intermolecular interactions with solutes, have been proposed as possible carbon capture media. To inform the choice of an optimal ionic liquid system, it can be useful to understand the details of dynamics and interactions on fundamental time scales (femtoseconds to picoseconds) of dissolved gases, particularly carbon dioxide (CO2), within the complex solvation structures present in these uniquely organized materials. The rotational and local structural fluctuation dynamics of CO2 in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2) were investigated by using ultrafast infrared spectroscopy to interrogate the CO2 asymmetric stretch. Polarization-selective pump probe measurements yielded the orientational correlation function of the CO2 vibrational transition dipole. It was found that reorientation of the carbon dioxide occurs on 3 time scales: 0.91 ± 0.03, 8.3 ± 0.1, 54 ± 1 ps. The initial two are attributed to restricted wobbling motions originating from a gating of CO2 motions by the IL cations and anions. The final (slowest) decay corresponds to complete orientational randomization. Two-dimensional infrared vibrational echo (2D IR) spectroscopy provided information on structural rearrangements, which cause spectral diffusion, through the time dependence of the 2D line shape. Analysis of the time-dependent 2D IR spectra yields the frequency-frequency correlation function (FFCF). Polarization-selective 2D IR experiments conducted on the CO2 asymmetric stretch in the parallel- and perpendicular-pumped geometries yield significantly different FFCFs due to a phenomenon known as reorientation-induced spectral diffusion (RISD), revealing strong vector interactions with the liquid structures that evolve slowly on the (independently measured) rotation time scales. To separate the RISD contribution to the FFCF from the structural spectral

  4. Ionic liquid based dispersive liquid-liquid microextraction for the extraction of pesticides from bananas.

    PubMed

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Asensio-Ramos, María; Rodríguez-Delgado, Miguel Angel

    2009-10-23

    This paper describes a dispersive liquid-liquid microextraction (DLLME) procedure using room temperature ionic liquids (RTILs) coupled to high-performance liquid chromatography with diode array detection capable of quantifying trace amounts of eight pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox and fenazaquin) in bananas. Fruit samples were first homogenized and extracted (1g) with acetonitrile and after suitable evaporation and reconstitution of the extract in 10 mL of water, a DLLME procedure using 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) as extraction solvent was used. Experimental conditions affecting the DLLME procedure (sample pH, sodium chloride percentage, ionic liquid amount and volume of disperser solvent) were optimized by means of an experimental design. In order to determine the presence of a matrix effect, calibration curves for standards and fortified banana extracts (matrix matched calibration) were studied. Mean recovery values of the extraction of the pesticides from banana samples were in the range of 69-97% (except for thiophanate-methyl and carbofuran, which were 53-63%) with a relative standard deviation lower than 8.7% in all cases. Limits of detection achieved (0.320-4.66 microg/kg) were below the harmonized maximum residue limits established by the European Union (EU). The proposed method, was also applied to the analysis of this group of pesticides in nine banana samples taken from the local markets of the Canary Islands (Spain). To the best of our knowledge, this is the first application of RTILs as extraction solvents for DLLME of pesticides from samples different than water. PMID:19700165

  5. Pesticide extraction from table grapes and plums using ionic liquid based dispersive liquid-liquid microextraction.

    PubMed

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Herrera-Herrera, Antonio V; Rodríguez-Delgado, Miguel Angel

    2009-12-01

    Room temperature ionic liquids (RTILs) have been used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the determination of eight multi-class pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox, and fenazaquin) in table grapes and plums. The developed method involves the combination of DLLME and high-performance liquid chromatography with diode array detection. Samples were first homogenized and extracted with acetonitrile. After evaporation and reconstitution of the extract in water containing sodium chloride, a quick DLLME procedure that used the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) and methanol was developed. The RTIL dissolved in a very small volume of acetonitrile was directed injected in the chromatographic system. The comparison between the calibration curves obtained from standards and from spiked sample extracts (matrix-matched calibration) showed the existence of a strong matrix effect for most of the analyzed pesticides. A recovery study was also developed with five consecutive extractions of the two types of fruits spiked at three concentration levels. Mean recovery values were in the range of 72-100% for table grapes and 66-105% for plum samples (except for thiophanate-methyl and carbofuran, which were 64-75% and 58-66%, respectively). Limits of detection (LODs) were in the range 0.651-5.44 microg/kg for table grapes and 0.902-6.33 microg/kg for plums, representing LODs below the maximum residue limits (MRLs) established by the European Union in these fruits. The potential of the method was demonstrated by analyzing 12 commercial fruit samples (six of each type). PMID:19779926

  6. Unraveling the heterogeneity in N butyl-N-methylpiperidinium trifluromethanesulfonimide ionic liquid by 1D and 2D NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tripathi, Neha; Saha, Satyen

    2014-06-01

    Room temperature ionic liquids are one of the most exciting classes of materials in the last decade. In particular piperidinium (PIP) cation based ionic liquid (IL) (such as PIP14NTf2) have found application in electrochemistry/batteries. In this Letter, 2D NMR (NOESY and HOESY) is employed for studying the interactions present between cations and anions. HOESY spectrum shows that fluorine of NTf2 unusually interacts with all proton of the cation (PIP14). Combined HOESY and NOESY indicate that NTf2 anion is distributed heterogeneously in liquid. Existence of micro heterogeneity in this important class of IL is proposed.

  7. Ionic liquid lubrication at electrified interfaces

    NASA Astrophysics Data System (ADS)

    Kong, Lingling; Huang, Wei; Wang, Xiaolei

    2016-06-01

    The lubrication performances of ionic liquids at electrified interfaces have been investigated by using a reciprocating sliding tribometer. Experimental results indicated that the lubricity of the confined ionic liquids was markedly affected by the application of external electric field and strong interface electric field strength could result in high friction. The influence was more pronounced for the ionic liquid with a shorter alkyl side chain in particular. The main reason of the friction increment might be ascribed to the electrically influenced surface adsorption where the charged ions were structured to form robust and ordered layers.

  8. Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

    2007-01-01

    Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

  9. Spatial-decomposition analysis of electrical conductivity in ionic liquid.

    PubMed

    Tu, Kai-Min; Ishizuka, Ryosuke; Matubayasi, Nobuyuki

    2014-12-28

    The electrical conductivity of room temperature ionic liquid (IL) is investigated with molecular dynamics simulation. A trajectory of 1 μs in total is analyzed for the ionic liquid [C4mim][NTf2] (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and the anion is also called TFSI or TFSA), and the ion motions are examined in direct connection to the conductivity within the framework formulated previously [K.-M. Tu, R. Ishizuka, and N. Matubayasi, J. Chem. Phys. 141, 044126 (2014)]. As a transport coefficient, the computed electrical conductivity is in fair agreement with the experiment. The conductivity is then decomposed into the autocorrelation term of Nernst-Einstein form and the cross-correlation term describing the two-body motions of ions, and the cross-correlation term is further decomposed spatially to incorporate the structural insights on ion configurations into the dynamic picture. It is observed that the ion-pair contribution to the conductivity is not spatially localized and extends beyond the first coordination shell. The extent of localization of the cross-correlation effect in the conductivity is in correspondence to that of the spatial correlation represented by radial distribution function, which persists over nanometer scale. PMID:25554167

  10. Comparing two tetraalkylammonium ionic liquids. II. Phase transitions.

    PubMed

    Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Ferreira, Fabio F; Costa, Fanny N; Giles, Carlos

    2016-06-14

    Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N1444][NTf2] experiences glass transition at low temperature, whereas [N1114][NTf2] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions. PMID:27306016

  11. Ionic liquids adsorbed cellulose electro active paper actuator

    NASA Astrophysics Data System (ADS)

    Mahadeva, Suresha K.; Nayak, Jyoti; Kim, Jaehwan

    2009-03-01

    Cellulose has been reported as a smart material that can be used as sensors and actuators. The cellulose smart material is termed as Electro-active paper (EAPap), which is made by regenerating cellulose. However, regeneration of cellulose resulted in reduced performance output of actuators at low humidity levels. To solve this drawback, EAPap bending actuators were made by activating wet cellulose films in three different room temperature ionic liquids BMIPF6, BMICL and BMIBF4. Results showed that the actuator performance was dependent on the type of anions in the ionic liquids and it was in the order of BF4 > Cl > PF6Â. BMIBF4 activated actuator showed the maximum displacement of 3.8 mm with low electrical power consumption at relatively low humidity level. Also, it found that, although size of PF6 anion is larger than BF4 anion it showed the low displacement output due to poor adsorption as indicated the FTIR analysis.

  12. Surface confined ionic liquid as a stationary phase for HPLC

    SciTech Connect

    Wang, Qian; Baker, Gary A; Baker, Sheila N; Colon, Luis

    2006-01-01

    Trimethoxysilane ionosilane derivatives of room temperature ionic liquids based on alkylimidazolium bromides were synthesized for attachment to silica support material. The derivatives 1-methyl-3-(trimethoxysilylpropyl)imidazolium bromide and 1-butyl-3-(trimethoxysilylpropyl)imidazolium bromide were used to modify the surface of 3 {micro}m diameter silica particles to act as the stationary phase for HPLC. The modified particles were characterized by thermogravimetric analysis (TGA) and {sup 13}C and {sup 29}Si NMR spectroscopies. The surface modification procedure rendered particles with a surface coverage of 0.84 {micro}mol m{sup -2} for the alkylimidazolium bromide. The ionic liquid moiety was predominantly attached to the silica surface through two siloxane bonds of the ionosilane derivative (63%). Columns packed with the modified silica material were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic carboxylic acids as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic interaction, and other electrostatic interactions.

  13. Comparing two tetraalkylammonium ionic liquids. II. Phase transitions

    NASA Astrophysics Data System (ADS)

    Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.; Ribeiro, Mauro C. C.; Ferreira, Fabio F.; Costa, Fanny N.; Giles, Carlos

    2016-06-01

    Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N1444][NTf2] experiences glass transition at low temperature, whereas [N1114][NTf2] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.

  14. Lithium-Air and ionic Liquids

    SciTech Connect

    Kellar, Michael

    2015-09-01

    The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to the typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.

  15. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

    PubMed Central

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

    2014-01-01

    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

  16. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

    NASA Astrophysics Data System (ADS)

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

    2014-02-01

    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70 % molar yield towards citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide.

  17. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal.

    PubMed

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

    2014-01-01

    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

  18. Self-interaction error in DFT-based modelling of ionic liquids.

    PubMed

    Lage-Estebanez, Isabel; Ruzanov, Anton; García de la Vega, José M; Fedorov, Maxim V; Ivaništšev, Vladislav B

    2016-01-21

    The modern computer simulations of potential green solvents of the future, involving the room temperature ionic liquids, heavily rely on density functional theory (DFT). In order to verify the appropriateness of the common DFT methods, we have investigated the effect of the self-interaction error (SIE) on the results of DFT calculations for 24 ionic pairs and 48 ionic associates. The magnitude of the SIE is up to 40 kJ mol(-1) depending on the anion choice. Most strongly the SIE influences the calculation results of ionic associates that contain halide anions. For these associates, the range-separated density functionals suppress the SIE; for other cases, the revPBE density functional with dispersion correction and triple-ζ Slater-type basis is suitable for computationally inexpensive and reasonably accurate DFT calculations. PMID:26690957

  19. Catalytic reactions in ionic liquids.

    PubMed

    Sheldon, R

    2001-12-01

    The chemical industry is under considerable pressure to replace many of the volatile organic compounds (VOCs) that are currently used as solvents in organic synthesis. The toxic and/or hazardous properties of many solvents, notably chlorinated hydrocarbons, combined with serious environmental issues, such as atmospheric emissions and contamination of aqueous effluents is making their use prohibitive. This is an important driving force in the quest for novel reaction media. Curzons and coworkers, for example, recently noted that rigorous management of solvent use is likely to result in the greatest improvement towards greener processes for the manufacture of pharmaceutical intermediates. The current emphasis on novel reaction media is also motivated by the need for efficient methods for recycling homogeneous catalysts. The key to waste minimisation in chemicals manufacture is the widespread substitution of classical 'stoichiometric' syntheses by atom efficient, catalytic alternatives. In the context of homogeneous catalysis, efficient recycling of the catalyst is a conditio sine qua non for economically and environmentally attractive processes. Motivated by one or both of the above issues much attention has been devoted to homogeneous catalysis in aqueous biphasic and fluorous biphasic systems as well as in supercritical carbon dioxide. Similarly, the use of ionic liquids as novel reaction media may offer a convenient solution to both the solvent emission and the catalyst recycling problem. PMID:12239988

  20. Encapsulated ionic liquids (ENILs): from continuous to discrete liquid phase.

    PubMed

    Palomar, Jose; Lemus, Jesus; Alonso-Morales, Noelia; Bedia, Jorge; Gilarranz, Miguel A; Rodriguez, Juan J

    2012-10-14

    Encapsulated ionic liquid (ENIL) material was developed, consisting of ionic liquid (IL) introduced into carbon submicrocapsules. ENILs contain >85% w/w of IL but discretized in submicroscopic encapsulated drops, drastically increasing the surface contact area with respect to the neat fluid. ENIL materials were here tested for gas separation processes, obtaining a drastic increase in mass transfer rate. PMID:22935733

  1. Task-Specific Ionic Liquids for Mars Exploration (Green Chemistry for a Red Planet)

    NASA Technical Reports Server (NTRS)

    Karr, L. J.; Curreri, P. A.; Paley, M. S.; Kaukler, W. F.; Marone, M. J.

    2012-01-01

    Ionic Liquids (ILs) are organic salts with low melting points that are liquid at or near room temperature. The combinations of available ions and task-specific molecular designability make them suitable for a huge variety of tasks. Because of their low flammability, low vapor pressure, and stability in harsh environments (extreme temperatures, hard vacuum) they are generally much safer and "greener" than conventional chemicals and are thus suitable for a wide range of applications that support NASA exploration goals. This presentation describes several of the ongoing applications that are being developed at MSFC.

  2. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

    NASA Astrophysics Data System (ADS)

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-09-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm-2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm-2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion).

  3. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes.

    PubMed

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-01-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li(+) depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm(-2) and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm(-2) for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li(+) transport) and single ionic ionomer (prevention of Li(+) depletion). PMID:26411701

  4. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

    PubMed Central

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-01-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

  5. Ionic liquid polyoxometalates as light emitting materials

    SciTech Connect

    Ortiz-acosta, Denisse; Del Sesto, Rico E; Scott, Brian; Bennett, Bryan L; Purdy, Geraldine M; Muenchausen, Ross E; Mc Kigney, Edward; Gilbertson, Robert

    2008-01-01

    The low melting point, negligible vapor pressure, good solubility, and thermal and chemical stability make ionic liquids useful materials for a wide variety of applications. Polyoxometalates are early transition metal oxygen clusters that can be synthesized in many different sizes and with a variety of heterometals. The most attractive feature of POMs is that their physical properties, in particular electrical, magnetic, and optical properties, can be easily modified following known procedures. It has been shown that POMs can exhibit cooperative properties, as superconductivity and energy transfer. POM ionic liquids can be obtained by selecting the appropliate cation. Different alkyl ammonium and alkyl phosphonium salts are being used to produce new POM ionic liquids together with organic or inorganic luminescent centers to design light emitting materials. Ammonium and phosphonium cations with activated, polymerizable groups are being used to further polymerize the ionic liquid into transparent, solid materials with high metal density.

  6. Room-temperature stabilization of nanoscale superionic Ag2Se

    NASA Astrophysics Data System (ADS)

    Hu, T.; Wittenberg, J. S.; Lindenberg, A. M.

    2014-10-01

    Superionic materials are multi-component solids in which one sub-lattice exhibits high ionic conductivity within a fixed crystalline structure. This is typically associated with a structural phase transition occurring significantly above room temperature. Here, through combined temperature-resolved x-ray diffraction and differential scanning calorimetry, we map out the nanoscale size-dependence of the Ag2Se tetragonal to superionic phase transition temperature and determine the threshold size for room-temperature stabilization of superionic Ag2Se. For the first time, clear experimental evidence for such stabilization of the highly ionic conducting phase at room temperature is obtained in ˜2 nm diameter spheres, which corresponds to a >100 °C suppression of the bulk phase transition temperature. This may enable technological applications of Ag2Se in devices where high ionic conductivity at room temperature is required.

  7. Room-temperature stabilization of nanoscale superionic Ag₂Se.

    PubMed

    Hu, T; Wittenberg, J S; Lindenberg, A M

    2014-10-17

    Superionic materials are multi-component solids in which one sub-lattice exhibits high ionic conductivity within a fixed crystalline structure. This is typically associated with a structural phase transition occurring significantly above room temperature. Here, through combined temperature-resolved x-ray diffraction and differential scanning calorimetry, we map out the nanoscale size-dependence of the Ag₂Se tetragonal to superionic phase transition temperature and determine the threshold size for room-temperature stabilization of superionic Ag2Se. For the first time, clear experimental evidence for such stabilization of the highly ionic conducting phase at room temperature is obtained in ∼2 nm diameter spheres, which corresponds to a >100 °C suppression of the bulk phase transition temperature. This may enable technological applications of Ag₂Se in devices where high ionic conductivity at room temperature is required. PMID:25249347

  8. Superbase-derived protic ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin; Baker, Gary A.

    2013-09-03

    Protic ionic liquids having a composition of formula (A.sup.-)(BH.sup.+) wherein A.sup.- is a conjugate base of an acid HA, and BH.sup.+ is a conjugate acid of a superbase B. In particular embodiments, BH.sup.+ is selected from phosphazenium species and guanidinium species encompassed, respectively, by the general formulas: ##STR00001## The invention is also directed to films and membranes containing these protic ionic liquids, with particular application as proton exchange membranes for fuel cells.

  9. Anomalous Wien Effects in Supercooled Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Patro, L. N.; Burghaus, O.; Roling, B.

    2016-05-01

    We have measured conductivity spectra of several supercooled monocationic and dicationic ionic liquids in the nonlinear regime by applying ac electric fields with large amplitudes up to about 180 kV /cm . Thereby, higher harmonic ac currents up to the 7th order were detected. Our results point to the existence of anomalous Wien effects in supercooled ionic liquids. Most ionic liquids studied here exhibit a conductivity-viscosity relation, which is close to the predictions of the Nernst-Einstein and Stokes-Einstein equations, as observed for classical strong electrolytes like KCl. These "strong" ionic liquids show a much stronger nonlinearity of the conductivity than classical strong electrolytes. On the other hand, the conductivity-viscosity relation of the ionic liquid [P6 ,6 ,6 ,14][Cl ] points to ion association effects. This "weak" ionic liquid shows a strength of the nonlinear effect, which is comparable to classical weak electrolytes. However, the nonlinearity increases quadratically with the field. We suggest that a theory for explaining these anomalies will have to go beyond the level of Coulomb lattice gas models.

  10. Anomalous Wien Effects in Supercooled Ionic Liquids.

    PubMed

    Patro, L N; Burghaus, O; Roling, B

    2016-05-01

    We have measured conductivity spectra of several supercooled monocationic and dicationic ionic liquids in the nonlinear regime by applying ac electric fields with large amplitudes up to about 180  kV/cm. Thereby, higher harmonic ac currents up to the 7th order were detected. Our results point to the existence of anomalous Wien effects in supercooled ionic liquids. Most ionic liquids studied here exhibit a conductivity-viscosity relation, which is close to the predictions of the Nernst-Einstein and Stokes-Einstein equations, as observed for classical strong electrolytes like KCl. These "strong" ionic liquids show a much stronger nonlinearity of the conductivity than classical strong electrolytes. On the other hand, the conductivity-viscosity relation of the ionic liquid [P_{6,6,6,14}][Cl] points to ion association effects. This "weak" ionic liquid shows a strength of the nonlinear effect, which is comparable to classical weak electrolytes. However, the nonlinearity increases quadratically with the field. We suggest that a theory for explaining these anomalies will have to go beyond the level of Coulomb lattice gas models. PMID:27203333

  11. Dual Ionic and Organic Nature of Ionic Liquids.

    PubMed

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids--a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  12. Single particle dynamics in ionic liquids of 1-alkyl-3-methylimidazolium cations.

    PubMed

    Urahata, Sérgio M; Ribeiro, Mauro C C

    2005-01-01

    Ionic dynamics in room temperature molten salts (ionic liquids) containing 1-alkyl-3-methylimidazolium cations is investigated by molecular-dynamics simulations. Calculations were performed with united atom models, which were used in a previous detailed study of the equilibrium structure of ionic liquids [S. M. Urahata and M. C. C. Ribeiro, J. Chem. Phys. 120, 1855 (2004)]. The models were used in a systematic study of the dependency of several single particle time correlation functions on anion size (F-, Cl-, Br-, and PF6-) and alkyl chain length (1-methyl-, 1-ethyl-, 1-butyl-, and 1-octyl-). Despite of large mass and size of imidazolium cations, they exhibit larger mean-square displacement than anions. A further detailed picture of ionic motions is obtained by using appropriate projections of displacements along the plane or perpendicular to the plane of the imidazolium ring. A clear anisotropy in ionic displacement is revealed, the motion on the ring plane and almost perpendicular to the 1-alkyl chain being the less hindered one. Similar projections were performed on velocity correlation functions, whose spectra were used to relate short time ionic rattling with the corresponding long time diffusive regime. Time correlation functions of cation reorientation and dihedral angles of the alkyl chains are discussed, the latter decaying much faster than the former. A comparative physical picture of time scales for distinct dynamical processes in ionic liquids is provided. PMID:15638602

  13. Single particle dynamics in ionic liquids of 1-alkyl-3-methylimidazolium cations

    NASA Astrophysics Data System (ADS)

    Urahata, Sérgio M.; Ribeiro, Mauro C. C.

    2005-01-01

    Ionic dynamics in room temperature molten salts (ionic liquids) containing 1-alkyl-3-methylimidazolium cations is investigated by molecular-dynamics simulations. Calculations were performed with united atom models, which were used in a previous detailed study of the equilibrium structure of ionic liquids [S. M. Urahata and M. C. C. Ribeiro, J. Chem. Phys. 120, 1855 (2004)]. The models were used in a systematic study of the dependency of several single particle time correlation functions on anion size (F-, Cl-, Br-, and PF6-) and alkyl chain length (1-methyl-, 1-ethyl-, 1-butyl-, and 1-octyl-). Despite of large mass and size of imidazolium cations, they exhibit larger mean-square displacement than anions. A further detailed picture of ionic motions is obtained by using appropriate projections of displacements along the plane or perpendicular to the plane of the imidazolium ring. A clear anisotropy in ionic displacement is revealed, the motion on the ring plane and almost perpendicular to the 1-alkyl chain being the less hindered one. Similar projections were performed on velocity correlation functions, whose spectra were used to relate short time ionic rattling with the corresponding long time diffusive regime. Time correlation functions of cation reorientation and dihedral angles of the alkyl chains are discussed, the latter decaying much faster than the former. A comparative physical picture of time scales for distinct dynamical processes in ionic liquids is provided.

  14. Electrorecovery of actinides at room temperature

    SciTech Connect

    Stoll, Michael E; Oldham, Warren J; Costa, David A

    2008-01-01

    There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we

  15. Ionic liquids--an overview.

    PubMed

    Jenkins, Harry Donald Brooke

    2011-01-01

    A virtually unprecedented exponential burst of activity resulted following the publication, in 1998, of an article by Michael Freeman (Freemantle, M. Chemical & Engineering News, 1998, March 30, 32), which speculated on the role and contribution that ionic liquids (ILs) might make in the future on the development of clean technology. Up until that time only a handful of researchers were routinely engaged in the study of ILs but frenzied activity followed that continues until the present day. Scientists from all disciplines related to Chemistry have now embarked on studies, including theoreticians who are immersed in the aim of improving the "designer role" so that they can tailor ILs to deliver specified properties. This article, whilst not in any sense attempting to be exhaustive, highlights the main features which characterise ILs, presenting these in a form readily assimilated by newcomers to this area of research. An extensive glossary is featured in this article as well as a chronological list which charts the major areas of development. What follows consists of a number of sections briefly describing the role of lLs as solvents, hypergolic fuels, their use in some electrochemical devices such as solar cells and lithium batteries and their use in polymerisation reactions, followed by a concise summary of some of the other roles that they are capable of playing. The role of empirical, volume-based thermodynamics procedures, as well as large scale computational studies on ILs is also highlighted. These developments which are described are remarkable in that they have been achieved in less than a decade and a half although knowledge of these materials has existed for much longer. PMID:22026149

  16. Electrochemical synthesis and surface characterization of poly(3,4-ethylenedioxythiophene) films grown in an ionic liquid.

    PubMed

    Ahmad, Shahzada; Deepa, M; Singh, S

    2007-11-01

    We report a facile method to synthesize poly(3,4-ethylenedioxythiophene) (PEDOT) films at room temperature in a waterproof ionic liquid, 1-ethyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide (EMIPFSI), by electropolymerization. The ionic liquid leads to the formation of randomly oriented nanofibers and particles confined to submicrometer-sized domains in the film microstructure. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) studies provide information about the intercalation of the cation apart from the reported anion in the polymer film, and on how the imidazolium ion controls the growth of PEDOT nanostructures. PMID:17915903

  17. Synthesis of monodisperse Cu nanoparticles in Ionic Liquids: A synthetic and catalytic approach of in situ nanoparticles

    NASA Astrophysics Data System (ADS)

    Mohan, Balaji; Woo, Hyunje; Jang, Seongwan; Lee, Seungwan; Park, Sungkyun; Park, Kang Hyun

    2013-08-01

    We described herein the importance of Ionic Liquids to synthesize in situ monodisperse copper nanoparticles with high surface area at room temperature. The in situ formed nanoparticles were characterized by Transmission Electron Microscopy (TEM), Energy-dispersive spectrometer (EDS) and X-ray powder diffraction (XRD) and shows excellent catalytic activity for cycloaddition reaction between azides with terminal alkynes to furnish 1,4-triazoles in excellent yields under mild conditions. The present catalytic system can take advantage of both ionic liquids and nanoparticles. The proposed catalytic system can minimize the time to synthesize copper nanoparticles with stabilizer and eliminates additional additives as well.

  18. A stable room-temperature sodium-sulfur battery

    NASA Astrophysics Data System (ADS)

    Wei, Shuya; Xu, Shaomao; Agrawral, Akanksha; Choudhury, Snehashis; Lu, Yingying; Tu, Zhengyuan; Ma, Lin; Archer, Lynden A.

    2016-06-01

    High-energy rechargeable batteries based on earth-abundant materials are important for mobile and stationary storage technologies. Rechargeable sodium-sulfur batteries able to operate stably at room temperature are among the most sought-after platforms because such cells take advantage of a two-electron-redox process to achieve high storage capacity from inexpensive electrode materials. Here we report a room-temperature sodium-sulfur battery that uses a microporous carbon-sulfur composite cathode, and a liquid carbonate electrolyte containing the ionic liquid 1-methyl-3-propylimidazolium-chlorate tethered to SiO2 nanoparticles. We show that these cells can cycle stably at a rate of 0.5 C (1 C=1675, mAh g-1) with 600 mAh g-1 reversible capacity and nearly 100% Coulombic efficiency. By means of spectroscopic and electrochemical analysis, we find that the particles form a sodium-ion conductive film on the anode, which stabilizes deposition of sodium. We also find that sulfur remains interred in the carbon pores and undergo solid-state electrochemical reactions with sodium ions.

  19. A stable room-temperature sodium-sulfur battery.

    PubMed

    Wei, Shuya; Xu, Shaomao; Agrawral, Akanksha; Choudhury, Snehashis; Lu, Yingying; Tu, Zhengyuan; Ma, Lin; Archer, Lynden A

    2016-01-01

    High-energy rechargeable batteries based on earth-abundant materials are important for mobile and stationary storage technologies. Rechargeable sodium-sulfur batteries able to operate stably at room temperature are among the most sought-after platforms because such cells take advantage of a two-electron-redox process to achieve high storage capacity from inexpensive electrode materials. Here we report a room-temperature sodium-sulfur battery that uses a microporous carbon-sulfur composite cathode, and a liquid carbonate electrolyte containing the ionic liquid 1-methyl-3-propylimidazolium-chlorate tethered to SiO2 nanoparticles. We show that these cells can cycle stably at a rate of 0.5 C (1 C=1675, mAh g(-1)) with 600 mAh g(-1) reversible capacity and nearly 100% Coulombic efficiency. By means of spectroscopic and electrochemical analysis, we find that the particles form a sodium-ion conductive film on the anode, which stabilizes deposition of sodium. We also find that sulfur remains interred in the carbon pores and undergo solid-state electrochemical reactions with sodium ions. PMID:27277345

  20. A stable room-temperature sodium–sulfur battery

    PubMed Central

    Wei, Shuya; Xu, Shaomao; Agrawral, Akanksha; Choudhury, Snehashis; Lu, Yingying; Tu, Zhengyuan; Ma, Lin; Archer, Lynden A.

    2016-01-01

    High-energy rechargeable batteries based on earth-abundant materials are important for mobile and stationary storage technologies. Rechargeable sodium–sulfur batteries able to operate stably at room temperature are among the most sought-after platforms because such cells take advantage of a two-electron-redox process to achieve high storage capacity from inexpensive electrode materials. Here we report a room-temperature sodium–sulfur battery that uses a microporous carbon–sulfur composite cathode, and a liquid carbonate electrolyte containing the ionic liquid 1-methyl-3-propylimidazolium-chlorate tethered to SiO2 nanoparticles. We show that these cells can cycle stably at a rate of 0.5 C (1 C=1675, mAh g−1) with 600 mAh g−1 reversible capacity and nearly 100% Coulombic efficiency. By means of spectroscopic and electrochemical analysis, we find that the particles form a sodium-ion conductive film on the anode, which stabilizes deposition of sodium. We also find that sulfur remains interred in the carbon pores and undergo solid-state electrochemical reactions with sodium ions. PMID:27277345

  1. Ultrasound-assisted solvent-free synthesis of lactic acid esters in novel SO3H-functionalized Brønsted acidic ionic liquids.

    PubMed

    Li, Xinzhong; Lin, Qi; Ma, Liang

    2010-06-01

    Mild and efficient Fischer esterification reactions of lactic acid with a variety of straight chain aliphatic alcohols, cyclohexanol and benzyl alcohol were successfully performed using two novel Brønsted acidic ionic liquids that bear an aromatic sulfonic acid group on the imidazolium or pyridinium cation under ultrasound irradiation. These reactions carried out smoothly with good to excellent conversion rate (78-96%) and satisfactory yields (73-92%) in shorter reaction time (4-6h) at room temperature when the amount of ionic liquids was 20 mol%. These ionic liquids could be recovered readily and recycled five times without any significant loss in their catalytic activity. PMID:20226709

  2. Ionic Liquids for Utilization of Waste Heat from Distributed Power Generation Systems

    SciTech Connect

    Joan F. Brennecke; Mihir Sen; Edward J. Maginn; Samuel Paolucci; Mark A. Stadtherr; Peter T. Disser; Mike Zdyb

    2009-01-11

    The objective of this research project was the development of ionic liquids to capture and utilize waste heat from distributed power generation systems. Ionic Liquids (ILs) are organic salts that are liquid at room temperature and they have the potential to make fundamental and far-reaching changes in the way we use energy. In particular, the focus of this project was fundamental research on the potential use of IL/CO2 mixtures in absorption-refrigeration systems. Such systems can provide cooling by utilizing waste heat from various sources, including distributed power generation. The basic objectives of the research were to design and synthesize ILs appropriate for the task, to measure and model thermophysical properties and phase behavior of ILs and IL/CO2 mixtures, and to model the performance of IL/CO2 absorption-refrigeration systems.

  3. Thermal decomposition mechanisms of alkylimidazolium ionic liquids with cyano-functionalized anions.

    PubMed

    Chambreau, Steven D; Schenk, Adam C; Sheppard, Anna J; Yandek, Gregory R; Vaghjiani, Ghanshyam L; Maciejewski, John; Koh, Christine J; Golan, Amir; Leone, Stephen R

    2014-11-26

    Because of the unusually high heats of vaporization of room-temperature ionic liquids (RTILs), volatilization of RTILs through thermal decomposition and vaporization of the decomposition products can be significant. Upon heating of cyano-functionalized anionic RTILs in vacuum, their gaseous products were detected experimentally via tunable vacuum ultraviolet photoionization mass spectrometry performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Experimental evidence for di- and trialkylimidazolium cations and cyano-functionalized anionic RTILs confirms thermal decomposition occurs primarily through two pathways: deprotonation of the cation by the anion and dealkylation of the imidazolium cation by the anion. Secondary reactions include possible cyclization of the cation and C2 substitution on the imidazolium, and their proposed reaction mechanisms are introduced here. Additional evidence supporting these mechanisms was obtained using thermal gravimetric analysis-mass spectrometry, gas chromatography-mass spectrometry, and temperature-jump infrared spectroscopy. In order to predict the overall thermal stability in these ionic liquids, the ability to accurately calculate both the basicity of the anions and their nucleophilicity in the ionic liquid is critical. Both gas phase and condensed phase (generic ionic liquid (GIL) model) density functional theory calculations support the decomposition mechanisms, and the GIL model could provide a highly accurate means to determine thermal stabilities for ionic liquids in general. PMID:25381899

  4. Electrolytes based on alkoxysilyl-functionalized ionic liquids: viscoelastic properties and conductivity.

    PubMed

    Slemenik Perše, L; Colović, M; Hajzeri, M; Orel, B; Surca Vuk, A

    2014-08-14

    Ionic liquids can be successfully used as electrolytes in electrochemical devices when they are in their quasi-solid state. Among several methods of solidification, a sol-gel process was chosen and a set of alkoxysilyl-functionalized iodide imidazolium-based ionic liquids were synthesized. The electrolytes were prepared by mixing these ionic liquids with a non-polymerisable ionic liquid (1-methyl-3-propylimidazolium iodide (MPIm(+)I(-))). Iodine was dissolved in an electrolyte matrix in order to form an I3(-)/I(-) redox couple. The change of the structure from sol to gel was followed by rheological tests in order to show the effect of different rheological parameters on the gelation process. The solvolysis with glacial acetic acid and condensation were followed by rheological experiments on the samples taken from a batch, and in situ on the rheometer. The formed three-dimensional sol-gel networks of various alkoxysilyl-functionalized ionic liquids differed in their microstructures and viscoelastic properties that were correlated with conductivity. The results show that the conductivity of approximately 10(-3) S cm(-1) at room temperature was achieved for the gels with relatively high values of elastic modulus and noticeable viscous contribution. It is shown that not only the viscosity but also the viscoelastic behavior and especially the relationship between viscous and elastic moduli (phase shift) together with the time of gelation are essential for the high conductivity of electrolytes. PMID:24955729

  5. Water in ionic liquids at electrified interfaces: the anatomy of electrosorption.

    PubMed

    Feng, Guang; Jiang, Xikai; Qiao, Rui; Kornyshev, Alexei A

    2014-11-25

    Complete removal of water from room-temperature ionic liquids is nearly impossible. For the electrochemical applications of ionic liquids, how water is distributed in the electrical double layers when the bulk liquids are not perfectly dry can potentially determine whether key advantages of ionic liquids, such as a wide electrochemical window, can be harnessed in practical systems. In this paper, we study the adsorption of water on electrode surfaces in contact with humid, imidazolium-based ionic liquids using molecular dynamics simulations. The results revealed that water molecules tend to accumulate within sub-nanometer distance from charged electrodes. At low amount of water in the bulk, the distributions of ions and of electrostatic potential in the double layer are affected weakly by the presence of water, but the spatial distribution of water molecules is strongly dependent on both. The preferential positions of water molecules in double layers are determined by the balance of several factors: the tendency to follow the positions of the maximal absolute value of the electrical field, the association with their ionic surroundings, and the propensity to settle at positions where more free space is available. The balance between these factors changes with charging the electrode, but the adsorption of water generally increases with voltage. The ion specificity of water electrosorption is manifested in the stronger presence of water near positive electrodes (where anions are the counterions) than near negative electrodes (where cations are counterions). These predictions await experimental verification. PMID:25341189

  6. [Determination of solubility parameters for asymmetrical dicationic ionic liquids by inverse gas chromatography].

    PubMed

    Wang, Jun; Yang, Xuzhao; Wu, Jinchao; Song, Hao; Zou, Wenyuan

    2015-12-01

    Inverse gas chromatographic (IGC) technology was used to determine the solubility parameters of three asymmetrical dicationic ionic liquids ([ PyC5Pi] [ NTf2]2, [MpC5Pi] [NTf2]2 and [PyC6Pi] [NTf2]2) at 343.15-363.15 K. Five alkanes were applied as test probes including octane (n-C8) , decane (n-C10), dodecane (n-C12), tetradecane (n-C14), hexadecane (n-C16). Some thermodynamic parameters were obtained by IGC data analysis, such as the specific retention volumes of the solvents (V0(g)), the molar enthalpies of sorption (ΔHs(1)), the partial molar enthalpies of mixing at infinite dilution (ΔH∞91)), the molar enthalpies of vaporization (ΔH)v)), the activity coefficients at infinite dilution (Ω∞(1)), and Flory-Huggins interaction parameters (χ∞(12)) between ionic liquids and probes. The solubility parameters (δ2) of the three dicationic ionic liquids at room temperature (298.15 K) were 28.52-32.66 (J x cm(-3)) ½. The solubility parameters (δ2) of cationic structure with 4-methyl morpholine are bigger than those of the cationic structure with pyridine. The bigger the solubility parameter (δ2) is, the more the carbon numbers of linking group of the ionic liquids are. The results are of great importance to the study of the solution behavior and the applications of ionic liquid. PMID:27097464

  7. Full-ionic liquid gel electrolytes: Enhanced photovoltaic performances in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Li, Qinghua; Tang, Qunwei; He, Benlin; Yang, Peizhi

    2014-10-01

    Liquid electrolytes containing redox species have been widely used in dye-sensitized solar cells (DSSCs), whereas the volatility of organic solvents has been a tremendous obstacle for their commercial application. To assemble durable DSSCs, here we report the synthesis of full-ionic liquid electrolyte, in which 1-butyl-3-methylimidazolium nitrate is employed as solvent and 1-methyl-3-propylimidazolium iodide is iodide source. Using the imbibition performance of amphiphilic poly(acrylic acid/gelatin) [poly(AA/GR)] and poly(acrylic acid/cetyltrimethyl ammonium bromide) [poly(AA/CTAB)] matrices, full-ionic liquid electrolytes are imbibed into three-dimensional framework of poly(AA/GR) or poly(AA/CTAB) to form stable gel electrolytes. Room-temperature ionic conductivities as high as 17.82 and 18.44 mS cm-1 are recorded from full-ionic liquid imbibed poly(AA/GR) and poly(AA/CTAB) gel electrolytes, respectively. Promising power conversion efficiencies of 7.19% and 7.15% are determined from their DSSC devices in comparison with 6.55% and 6.12% from traditional acetonitrile-based poly(AA/GR) and poly(AA/CTAB) gel electrolytes, respectively. The new concept along with easy fabrication demonstrates the full-ionic liquid electrolytes to be good alternatives for robust gel electrolytes in quasi-solid-state DSSCs.

  8. Mesoporous silica/ionic liquid quasi-solid-state electrolytes and their application in lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Zhang, Zhengxi; Yin, Kun; Yang, Li; Tachibana, Kazuhiro; Hirano, Shin-ichi

    2015-03-01

    In this work, the ordered mesoporous silica, SBA-15, is chosen as the matrix for the first time to prepare quasi-solid-state electrolytes (QSSEs) with an ionic liquid, LiTFSI salt and PVdF-HFP. The as-obtained QSSEs are evaluated by electrochemical methods. Lithium metal batteries containing these QSSEs exhibit high discharge capacity and good cycle performance at room temperature, indicating successful battery operation.

  9. Key Developments in Ionic Liquid Crystals

    PubMed Central

    Alvarez Fernandez, Alexandra; Kouwer, Paul H. J.

    2016-01-01

    Ionic liquid crystals are materials that combine the classes of liquid crystals and ionic liquids. The first one is based on the multi-billion-dollar flat panel display industry, whilst the latter quickly developed in the past decades into a family of highly-tunable non-volatile solvents. The combination yields materials with a unique set of properties, but also with many challenges ahead. In this review, we provide an overview of the key concepts in ionic liquid crystals, particularly from a molecular perspective. What are the important molecular parameters that determine the phase behavior? How should they be introduced into the molecules? Finally, which other tools does one have to realize specific properties in the material? PMID:27196890

  10. Dual Ionic and Organic Nature of Ionic Liquids

    PubMed Central

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  11. Dual Ionic and Organic Nature of Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs.

  12. Ionic Liquid Extractions of Soil Organic Matter

    NASA Astrophysics Data System (ADS)

    Patti, Antonio; Macfarlane, Douglas; Clarke, Michael

    2010-05-01

    A large range of ionic liquids with the ability to dissolve different classes of natural biopolymers (e.g. cellulose, lignin, protein) have been reported in the literature. These have the potential to isolate different fractions of soil organic matter, thus yielding novel information that is not available through other extraction procedures. The ionic liquids dimethylammonium dimethylcarbamate (DIMCARB), alkylbenzenesulfonate and 1-butyl-3methylimidazolium chloride (Bmim Cl) can solubilise selected components of soil organic matter. Soil extractions with these materials showed that the organic matter recovered showed chemical properties that were consistent with humic substances. These extracts had a slightly different organic composition than the humic acids extracted using the traditional International Humic Substances Society (IHSS) method. The ionic liquids also solubilised some inorganic matter from the soil. Humic acids recovered with alkali were also partially soluble in the ionic liquids. DIMCARB appeared to chemically interfere with organic extract, increasing the level of nitrogen in the sample. It was concluded that the ionic liquid Bmim Cl may function as a useful solvent for SOM, and may be used to recover organic matter of a different character to that obtained with alkali

  13. Physicochemical Properties of Imidazolium-derived Ionic Liquids with Different C-2 Substitutions

    SciTech Connect

    Liao, Chen; Shao, Nan; Han, Kee Sung; Sun, Xiao-Guang; Jiang, Deen; Hagaman, Edward {Ed} W; Dai, Sheng

    2011-01-01

    Five room temperature ionic liquids based on C-2 substituted imidazolium cations and bis(trifluoromethanesulfonyl)imide (TFSI) anion were synthesized and their physicochemical properties: thermal property, density, viscosity, ionic conductivity, self-diffusion coefficients, and electrochemical stability were systematically investigated. The temperature dependence of both viscosity and ionic conductivities of these ionic liquids can be described by Vogel-Fulcher-Tamman (VFT) equation. Compared with the reference, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, the introduction of functional groups at the C-2 position generally increased the viscosity and lowered the ionic conductivity. The introduction of ether group ( CH2OCH2CH2CH2CH3) at the C-2 position not only enhanced the reduction stability of the ionic liquids but also exhibited the lowest solid electrolyte interfacial resistance (RSEI). On the contrary, the introduction of a cyano group ( CN) at the C-2 position not only decreased the reduction stability but also adversely increased the SEI resistance. The effect of the C-2 substitution on the reduction stability was explained by the change of the energy level of the lowest unoccupied molecular orbital. The self-diffusion coefficients (D) of each ion were measured by pulsed field gradient nuclear magnetic resonance (PFG-NMR). The lithium transference number (tLi) of 0.5 M LiTFSI/IL solutions calculated from the self-diffusion coefficients was in the range of 0.04 and 0.09.

  14. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    NASA Astrophysics Data System (ADS)

    Cha, E. H.; Lim, S. A.; Park, J. H.; Kim, D. W.; Macfarlane, D. R.

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N, N-dimethyl- N-propyl- N-butyl ammonium tricyanomethanide (N 1134TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 × 10 -3 S cm -1 at 25 °C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 × 10 -3 S cm -1 at 25 °C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N 1134TCM (2.48 × 10 -3 S cm -1). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N 1134TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species.

  15. Hydrogen production by water electrolysis using tetra-alkyl-ammonium-sulfonic acid ionic liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Fiegenbaum, Fernanda; Martini, Emilse M.; de Souza, Michèle O.; Becker, Márcia R.; de Souza, Roberto F.

    2013-12-01

    Triethylammonium-propanesulfonic acid tetrafluoroborate (TEA-PS·BF4) is used as an electrolyte in the water electrolysis. The electrolysis of water with this ionic conductor produces high current densities with high efficiencies, even at room temperatures. A system using TEA-PS·BF4 in an electrochemical cell with platinum electrodes has current densities (i) up to 1.77 A cm-2 and efficiencies between 93 and 99% in temperatures ranging from 25 °C to 80 °C. The activation energy observed with TEA-PS·BF4 is ca. 9.3 kJ mol-1, a low value that can be explained by the facilitation of proton transport in the organised aqueous ionic liquid media. The unexpectedly high efficiency of this system is discussed by taking into account the high conductivities associated with the Brönsted and Lewis acidity characteristics associated with these ionic conductive materials.

  16. Fluorescence Correlation Spectroscopy Evidence for Structural Heterogeneity in Ionic Liquids

    SciTech Connect

    Guo, Jianchang; Baker, Gary A; Hillesheim, Patrick C; Dai, Sheng; Shaw, Robert W; Mahurin, Shannon Mark

    2011-01-01

    Self-aggregation in room temperature ionic liquids (RTILs) has been a subject of intense interest in recent years. In this work, we provide new experimental evidence for chain length-dependent self-aggregation in RTILs using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [CnMPy][Tf2N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decrease with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chained [CnMPy][Tf2N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [CnMPy]+. The presence of this local liquid structuring provides important insight into the behavior of RTILs relevant to their application in photovoltaics, fuel cells, and batteries.

  17. Unusual redox stability of neptunium in the ionic liquid [Hbet][Tf(2)N].

    PubMed

    Long, Kristy; Goff, George; Runde, Wolfgang

    2014-07-25

    The behavior of neptunium in the ionic liquid betaine bistriflimide, [Hbet][Tf2N], has been studied spectroscopically at room temperature and 60 °C for the first time. An unprecedented complex redox chemistry is observed, with up to three oxidation states (iv, v and vi) and up to six Np species existing simultaneously. Both redox reactions and coordination of betaine are observed for Np(iv), (v) and (vi). Elevating the temperature accelerates the coordination of Np(v) with betaine and reduction reactions slow down. PMID:24752760

  18. Ionic Liquid Promoted Diazenylation of N-Heterocyclic Compounds with Aryltriazenes under Mild Conditions.

    PubMed

    Cao, Dawei; Zhang, Yonghong; Liu, Chenjiang; Wang, Bin; Sun, Yadong; Abdukadera, Ablimit; Hu, Haiyan; Liu, Qiang

    2016-05-01

    An efficient, mild, and metal-free approach to direct diazenylation of N-heterocyclic compounds with aryltriazenes using Brønsted ionic liquid as a promoter has been developed for the first time. Many N-heterocyclic azo compounds were synthesized in good to excellent yields at room temperature under an open atmosphere. Notably, the promoter 1,3-bis(4-sulfobutyl)-1H-imidazol-3-ium hydrogen sulfate could be conveniently recycled and reused with the same efficacies for at least four cycles. PMID:27096379

  19. Energy Efficient Electrochromic Windows Incorporating Ionic Liquids

    SciTech Connect

    Cheri Boykin; James Finley; Donald Anthony; Julianna Knowles; Richard Markovic; Michael Buchanan; Mary Ann Fuhry; Lisa Perrine

    2008-11-30

    One approach to increasing the energy efficiency of windows is to control the amount of solar radiation transmitted through a window by using electrochromic technology. What is unique about this project is that the electrochromic is based on the reduction/oxidation reactions of cathodic and anodic organic semi-conducting polymers using room temperature ionic liquids as ion transport electrolytes. It is believed that these types of coatings would be a lower cost alternative to traditional all inorganic thin film based electrochromic technologies. Although there are patents1 based on the proposed technology, it has never been reduced to practice and thoroughly evaluated (i.e. durability and performance) in a window application. We demonstrate that by using organic semi-conductive polymers, specific bands of the solar spectrum (specifically visible and near infrared) can be targeted for electrochemical variable transmittance responsiveness. In addition, when the technology is incorporated into an insulating glass unit, the energy parameters such as the solar heat gain coefficient and the light to solar gain ratio are improved over that of a typical insulating glass unit comprised of glass with a low emissivity coating. A minimum of {approx}0.02 quads of energy savings per year with a reduction of carbon emissions for electricity of {approx}320 MKg/yr benefit is achieved over that of a typical insulating glass unit including a double silver low-E coating. Note that these values include a penalty in the heating season. If this penalty is removed (i.e. in southern climates or commercial structures where cooling is predominate year-round) a maximum energy savings of {approx}0.05 quad per year and {approx}801 MKg/yr can be achieved over that of a typical insulating glass unit including a double silver low-E coating. In its current state, the technology is not durable enough for an exterior window application. The primary downfall is that the redox chemistry fails to

  20. Enzyme activity in dialkyl phosphate ionic liquids.

    PubMed

    Thomas, Marie F; Li, Luen-Luen; Handley-Pendleton, Jocelyn M; van der Lelie, Daniel; Dunn, John J; Wishart, James F

    2011-12-01

    The activity of four metagenomic enzymes and an enzyme cloned from the straw mushroom, Volvariella volvacea were studied in the following ionic liquids, 1,3-dimethylimidazolium dimethyl phosphate, [mmim][dmp], 1-ethyl-3-methylimidazolium dimethyl phosphate, [emim][dmp], 1-ethyl-3-methylimidazolium diethyl phosphate, [emim][dep] and 1-ethyl-3-methylimidazolium acetate, [emim][OAc]. Activity was determined by analyzing the hydrolysis of para-nitrobenzene carbohydrate derivatives. In general, the enzymes were most active in the dimethyl phosphate ionic liquids, followed by acetate. Generally speaking, activity decreased sharply for concentrations of [emim][dep] above 10% v/v, while the other ionic liquids showed less impact on activity up to 20% v/v. PMID:22001053

  1. Enzyme activity in dialkyl phosphate ionic liquids

    SciTech Connect

    Thomas, M.F.; Dunn, J.; Li, L.-L.; Handley-Pendleton, J. M.; van der lelie, D.; Wishart, J. F.

    2011-12-01

    The activity of four metagenomic enzymes and an enzyme cloned from the straw mushroom, Volvariellavolvacea were studied in the following ionic liquids, 1,3-dimethylimidazolium dimethyl phosphate, [mmim][dmp], 1-ethyl-3-methylimidazolium dimethyl phosphate, [emim][dmp], 1-ethyl-3-methylimidazolium diethyl phosphate, [emim][dep] and 1-ethyl-3-methylimidazolium acetate, [emim][OAc]. Activity was determined by analyzing the hydrolysis of para-nitrobenzene carbohydrate derivatives. In general, the enzymes were most active in the dimethyl phosphate ionic liquids, followed by acetate. Generally speaking, activity decreased sharply for concentrations of [emim][dep] above 10% v/v, while the other ionic liquids showed less impact on activity up to 20% v/v.

  2. Desulfurization of oxidized diesel using ionic liquids

    NASA Astrophysics Data System (ADS)

    Wilfred, Cecilia D.; Salleh, M. Zulhaziman M.; Mutalib, M. I. Abdul

    2014-10-01

    The extraction of oxidized sulfur compounds from diesel were carried out using ten types of ionic liquids consisting of different cation and anion i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazoium thiocyanate, 1-butyl-3-methylimidazoium dicyanamide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, trioctylmethylammonium chloride, 1-propionitrile-3-butylimidazolium thiocyanate, 1-propionitrile-3-butylimidazolium dicyanamide and 1-butyl-6-methylquinolinium dicyanamide. The oxidation of diesel was successfully done using phosphotungstic acid as the catalyst, hydrogen peroxide (H2O2) as the oxidant and trioctylmethylammonium chloride as the phase transfer agent. The oxidation of diesel changes the sulfur compounds into sulfone which increases its polarity and enhances the ionic liquid's extraction performance. Result showed that ionic liquid [C4mquin][N(CN)2] performed the highest sulfur removal (91% at 1:5 diesel:IL ratio) compared to the others.

  3. TETRAALKYLPHOSPHONIUM POLYOXOMETALATES AS NOVEL IONIC LIQUIDS.

    SciTech Connect

    DIETZ,M.L.; RICKERT, P.G.; ANTONIO, M.R.; FIRESTONE, M.A.; WISHART, J.F.; SZREDER, T.

    2007-11-30

    The pairing of a Lindqvist or Keggin polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation, [R{sub 3}R{prime}P]{sup +}, has been shown to yield an original family of ionic liquids (POM-ILs), among them salts liquid at or near ambient temperature. The physicochemical properties of several such 'inorganic liquids', in particular their thermal properties, suggests the possible application of these compounds as robust, thermally-stable solvents for liquid-liquid extraction. A preliminary evaluation of the potential of POM-ILs in this application is presented.

  4. Evaluation of Vapor Pressure and Ultra-High Vacuum Tribological Properties of Ionic Liquids (2) Mixtures and Additives

    NASA Technical Reports Server (NTRS)

    Morales, Wilfredo; Koch, Victor R.; Street, Kenneth W., Jr.; Richard, Ryan M.

    2008-01-01

    Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.

  5. Taylor cones of ionic liquids from capillary tubes as sources of pure ions: The role of surface tension and electrical conductivity

    NASA Astrophysics Data System (ADS)

    Garoz, D.; Bueno, C.; Larriba, C.; Castro, S.; Romero-Sanz, I.; Fernandez de la Mora, J.; Yoshida, Y.; Saito, G.

    2007-09-01

    The emissions of Taylor cones from a wide range of ionic liquids (ILs) have been tested in vacuo in an attempt to identify what physical properties favor the purely ionic regime (PIR). This regime is well known in the case of Taylor cones of liquid metals. For nonmetallic liquids, it has been previously observed in conventional (capillary tube) electrospray sources at room temperature only for the room temperature molten salt (ionic liquid) EMI -BF4 (EMI =1-ethyl-3-methylimidazolium). A large number of other ILs and their mixtures have been studied here, most of which (but not all) are unable to reach the PIR at room temperature. Based on these results and additional theoretical considerations, strong support is assembled for the notion that the PIR is favored by ILs not only of high electrical conductivity but also of high surface tension. This hypothesis is confirmed by tests with three recently synthesized ILs, EMI -GaCl4, EMI -C(CN)3, and EMI -N(CN)2, all of which combine exceptional surface tension and electrical conductivity, and all of which reach the PIR at room temperature far more readily than EMI -BF4.

  6. Unravelling nanoconfined films of ionic liquids

    SciTech Connect

    Lee, Alpha A.; Vella, Dominic; Goriely, Alain; Perkin, Susan

    2014-09-07

    The confinement of an ionic liquid between charged solid surfaces is treated using an exactly solvable 1D Coulomb gas model. The theory highlights the importance of two dimensionless parameters: the fugacity of the ionic liquid, and the electrostatic interaction energy of ions at closest approach, in determining how the disjoining pressure exerted on the walls depends on the geometrical confinement. Our theory reveals that thermodynamic fluctuations play a vital role in the “squeezing out” of charged layers as the confinement is increased. The model shows good qualitative agreement with previous experimental data, with all parameters independently estimated without fitting.

  7. Effect of confinement on ionic liquid molecules in porous polymeric network

    NASA Astrophysics Data System (ADS)

    Raut, Prasad; Yuan, Shichen; Miyoshi, Toshikazu, , Dr.; Jana, Sadhan, , Dr.

    Ionic liquids (ILs) have attractive physicochemical properties but their room temperature liquid state necessitates pairing of IL with other solid, porous materials for fabrication of devices. Such materials are called ionogels. Loading of bulky IL molecules in the pores can dramatically affect the physical properties as function of the pore surface chemistry, pore size, and IL polarity. In this study porous syndiotactic polystyrene (sPS) network was made via thermos-reversible gelation. 1-Butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) is incorporated into the pores of sPS. DSC study and the temperature dependence of 13C-CPMAS NMR show that on confinement; the melting point of PYR14TFSI contained in the ionogel increased in comparison to the bulk PYR14TFSI. At room temperature, WAXD study of the ionogels showed diffraction pattern for PYR14TFSI in nanopores, correspondingly 1H NOESY experiments show strong non-bonded cation-cation correlation in ionogels. The results for the bulk IL does not show non-bonded correlation at room temperature, this increment of local order in ionogel might be the results of crystallization of IL molecules in confined geometry.

  8. Saturation properties of 1-alkyl-3-methylimidazolium based ionic liquids.

    PubMed

    Rane, Kaustubh S; Errington, Jeffrey R

    2014-07-24

    We study the liquid-vapor saturation properties of room temperature ionic liquids (RTILs) belonging to the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) using Monte Carlo simulation. We examine the effect of temperature and cation alkyl chain length n on the saturated densities, vapor pressures, and enthalpies of vaporization. These properties are explicitly calculated for temperatures spanning from 280 to 1000 K for RTILs with n = 2, 4, 6, 8, 10, and 12. We also explore how the identity of the anion influences saturation properties. Specifically, we compare results for [C(4)mim][NTf2] with those for 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]). Simulations are completed with a recently developed realistic united-atom force field. A combination of direct grand canonical and isothermal-isobaric temperature expanded ensemble simulations are used to construct phase diagrams. Our results are compared with experimental data and Gibbs ensemble simulation data. Overall, we find good agreement between our results and those measured experimentally. We find that the vapor pressures and enthalpies of vaporization show a strong dependence on the size of the alkyl chain at low temperatures, whereas no particular trend is observed at high temperatures. Finally, we also discuss the effect of temperature on liquid phase nanodomains observed in RTILs with large hydrophobic groups. We do not observe a drastic change in liquid phase structure upon variation of the temperature, which suggests there is not a sharp phase transition between a nanostructured and homogeneous liquid, as has been suggested in earlier studies. PMID:24986360

  9. Anion effects in the extraction of lanthanide 2-thenoyltrifluoroacetone complexes into an ionic liquid

    SciTech Connect

    Jensen, Mark P.; Beitz, James V.; Rickert, Paul G.; Borkowski, Marian; Laszak, Ivan; Dietz, Mark L.

    2012-07-01

    The extraction of trivalent lanthanides from an aqueous phase containing 1 M NaClO{sub 4} into the room temperature ionic liquid 1-butyl-3-methylimidazolium nonafluoro-1-butane sulfonate by the beta-diketone extractant 2-thenoyltrifluoroacetone (Htta) was studied. Radiotracer distribution, absorption spectroscopy, time-resolved laser-induced fluorescence spectroscopy, and X-ray absorption fine structure measurements point to the extraction of multiple lanthanide species. At low extractant concentrations, fully hydrated aqua cations of the lanthanides are present in the ionic liquid phase. As the extractant concentration is increased 1:2 and 1:3 lanthanide:tta species are observed. In contrast, 1:4 Ln:tta complexes were observed in the extraction of lanthanides by Htta into 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. (authors)

  10. Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

    PubMed

    Song, Yingying; Cheng, Chen; Jing, Huanwang

    2014-09-26

    Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. PMID:25154312

  11. Capacitive Energy Storage from - 50o to 100o Using an Ionic Liquid Electrolyte

    SciTech Connect

    Lin, Rongying; Taberna, Pierre-Louis; Santini, Sebastien; Presser, Volker; Perez, Carlos R.; Malbosc, Francois; Rupesinghe, Nalin L.; Teo, Kenneth B. K.; Gogotsi, Yury G.; Simon, Patrice

    2011-01-01

    Relying on redox reactions, most batteries are limited in their ability to operate at very low or very high temperatures. While performance of electrochemical capacitors is less dependent on the temperature, present-day devices still cannot cover the entire range needed for automotive and electronics applications under a variety of environmental conditions. We show that the right combination of the exohedral nanostructured carbon (nanotubes and onions) electrode and a eutectic mixture of ionic liquids can dramatically extend the temperature range of electrical energy storage, thus defying the conventional wisdom that ionic liquids can only be used as electrolytes above room temperature. We demonstrate electrical double layer capacitors able to operate from 50 to 100 C over a wide voltage window (up to 3.7 V) and at very high charge/discharge rates of up to 20 V/s.

  12. Testing Fundamental Properties of Ionic Liquids for Colloid Microthruster Applications

    NASA Technical Reports Server (NTRS)

    Anderson, John R.; Plett, Gary; Anderson, Mark; Ziemer, John

    2006-01-01

    NASA's New Millennium Program is scheduled to test a Disturbance Reduction System (DRS) on Space Technology 7 (ST7) as part of the European Space Agency's (ESA's) LISA Pathfinder Mission in late 2009. Colloid Micronewton Thrusters (CMNTs) will be used to counteract forces, mainly solar photon pressure, that could disturb gravitational reference sensors as part of the DRS. The micronewton thrusters use an ionic liquid, a room temperature molten salt, as propellant. The ionic liquid has a number of unusual properties that have a direct impact on thruster design. One of the most important issues is bubble formation before and during operation, especially during rapid pressure transitions from atmospheric to vacuum conditions. Bubbles have been observed in the feed system causing variations in propellant flow rate that can adversely affect thruster control. Bubbles in the feed system can also increase the likelihood that propellant will spray onto surfaces that can eventually lead to shorting high voltage electrodes. Two approaches, reducing the probability of bubble formation and removing bubbles with a new bubble eliminator device in the flow system, were investigated at Busek Co., Inc. and the Jet Propulsion Laboratory (JPL) to determine the effectiveness of both approaches. Results show that bubble formation is mainly caused by operation at low pressure and volatile contaminants in the propellant coming out of solution. A specification for the maximum tolerable level of contamination has been developed, and procedures for providing system cleanliness have been tested and implemented. The bubble eliminator device has also been tested successfully and has been implemented in recent thruster designs at Busek. This paper focuses on the propellant testing work at JPL, including testing of a breadboard level bubble eliminator device.

  13. Activation and stabilization of enzymes in ionic liquids.

    PubMed

    Moniruzzaman, Muhammad; Kamiya, Noriho; Goto, Masahiro

    2010-06-28

    As environmentally benign "green" solvents, room temperature ionic liquids (ILs) have been used as solvents or (co)solvents in biocatalytic reactions and processes for a decade. The technological utility of enzymes can be enhanced greatly by their use in ionic liquids (ILs) rather than in conventional organic solvents or in their natural aqueous reaction media. In fact, the combination of green properties and unique tailor-made physicochemical properties make ILs excellent non-aqueous solvents for enzymatic catalysis with numerous advantages over other solvents, including high conversion rates, high selectivity, better enzyme stability, as well as better recoverability and recyclability. However, in many cases, particularly in hydrophilic ILs, enzymes show relative instability and/or lower activity compared with conventional solvents. To improve the enzyme activity as well as stability in ILs, various attempts have been made by modifying the form of the enzymes. Examples are enzyme immobilization onto support materials via adsorption or multipoint attachment, lyophilization in the presence of stabilizing agents, chemical modification with stabilizing agents, formation of cross-linked enzyme aggregates, pretreatment with polar organic solvents or enzymes combined with suitable surfactants to form microemulsions. The use of these enzyme preparations in ILs can dramatically increase the solvent tolerance, enhance activity as well as stability, and improve enantioselectivity. This perspective highlights a number of pronounced strategies being used successfully for activation and stabilization of enzymes in non-aqueous ILs media. This review is not intended to be comprehensive, but rather to present a general overview of the potential approaches to activate enzymes for diverse enzymatic processes and biotransformations in ILs. PMID:20445940

  14. Observation of Charge Inversion of an Ionic Liquid at the Solid Salt-Liquid Interface by Sum Frequency Generation Spectroscopy.

    PubMed

    Peñalber, Chariz Y; Baldelli, Steven

    2012-04-01

    Sum frequency generation (SFG) vibrational spectroscopy of the ionic liquid, 1-butyl-3-methylimidazolium dicyanamide [BMIM][DCA], in contact with two different solid salt surfaces, BaF2(111) single crystal and solid NaCl{100}, are discussed in this Letter. This investigation describes the nature of an ionic liquid-(solid) salt interface using SFG, contributing a new understanding to the molecular-level interactions involved in salts, which are conceptually similar compounds (of purely ionic character) but of different physical properties (liquid versus solid at room temperature). Results show the presence of [BMIM](+) at the NaCl{100} surface and [DCA](-) at the BaF2(111) surface. [BMIM](+) cations adhere closely via Coulombic interactions to the negatively charged NaCl{100} surface, while [DCA](-) anions subsequently have a strong electrostatic affinity to the positively charged BaF2(111) surface. Ions of the ionic liquid adsorb to the solid salt surface to form a Helmholtz-like electric double layer. PMID:26286408

  15. Ionic Liquids and New Proton Exchange Membranes for Fuel Cells

    NASA Technical Reports Server (NTRS)

    Belieres, Jean-Philippe

    2004-01-01

    There is currently a great surge of activity in fuel cell research as laboratories across the world seek to take advantage of the high energy capacity provided by &el cells relative to those of other portable electrochemical power systems. Much of this activity is aimed at high temperature fie1 cells, and a vital component of such &el cells must be the availability of a high temperature stable proton-permeable membrane. NASA Glenn Research Center is greatly involved in developing this technology. Other approaches to the high temperature fuel cell involve the use of single- component or almost-single-component electrolytes that provide a path for protons through the cell. A heavily researched case is the phosphoric acid fuel cell, in which the electrolyte is almost pure phosphoric acid and the cathode reaction produces water directly. The phosphoric acid fie1 cell delivers an open circuit voltage of 0.9 V falling to about 0.7 V under operating conditions at 170 C. The proton transport mechanism is mainly vehicular in character according to the viscosity/conductance relation. Here we describe some Proton Transfer Ionic Liquids (PTILs) with low vapor pressure and high temperature stability that have conductivities of unprecedented magnitude for non-aqueous systems. The first requirement of an ionic liquid is that, contrary to experience with most liquids consisting of ions, it must have a melting point that is not much above room temperature. The limit commonly suggested is 100 C. PTILs constitute an interesting class of non-corrosive proton-exchange electrolyte, which can serve well in high temperature (T = 100 - 250 C) fuel cell applications. We will present cell performance data showing that the open circuit voltage output, and the performance of a simple H2(g)Pt/PTIL/Pt/O2(g) fuel cell may be superior to those of the equivalent phosphoric acid electrolyte fuel cell both at ambient temperature and temperatures up to and above 200 C. My work at NASA Glenn Research

  16. EXPEDITIOUS SYNTHESIS OF IONIC LIQUIDS USING ULTRASOUND AND MICROWAVE IRRADIATION

    EPA Science Inventory

    Environmentally friendlier preparations of ionic liquids have been developed that proceed expeditiously under the influence of microwave or ultrasound irradiation conditions using neat reactants, alkylimidazoles and alkyl halides. A number of useful ionic liquids have been prepar...

  17. Solvation and Reaction in Ionic Liquids

    SciTech Connect

    Maroncelli, Mark

    2015-01-15

    The long-range goal of our DOE-sponsored research is to obtain a fundamental understanding of solvation effects on photo-induced charge transfer and related processes. Much of the focus during the past funding period has been on studies of ionic liquids and on characterizing various reactions with which to probe the nature of this interesting new solvent medium.

  18. Cellulose regeneration and spinnability from ionic liquids.

    PubMed

    Hauru, Lauri K J; Hummel, Michael; Nieminen, Kaarlo; Michud, Anne; Sixta, Herbert

    2016-02-01

    Ionic liquid solutions of cellulose or dopes can be spun into Lyocell-type textile fibers by dry-jet wet spinning. An extruded dope is drawn over an air gap into water, where the water hydrates the ionic liquid and cellulose is regenerated. Spinnability studies have concentrated on the deformation and failure modes in the air gap and thus the rheology of the unhydrated spinning dope. Herein, a breach in the bath, another failure mode, is discussed. Dopes are prepared from the good spinning solvents NMMO·H2O and [DBNH]OAc and the poor spinning solvents [emim]OAc and [TMGH]OAc. The diffusion constants for water diffusing inwards and for ionic liquid diffusing outwards the emerging filament are measured offline. The resiliences and strengths of cellulose-ionic liquid solutions with different hydration stoichiometries are measured by means of rheometry. By calculating the diffusion dynamics, the resilience distribution of the forming filament is simulated. Gel strength distribution accounts for the tendency of [emim]OAc dopes to undergo a telescope-type breach, whereas the gelatinous solution state of [TMGH]OAc dopes accounts for their poor spinnability. PMID:26660047

  19. Carbon dioxide in ionic liquid microemulsions.

    PubMed

    Zhang, Jianling; Han, Buxing; Li, Jianshen; Zhao, Yueju; Yang, Guanying

    2011-10-10

    Tailor-made emulsion: a CO(2) -in-ionic-liquid microemulsion was produced for the first time. The CO(2)-swollen micelles are "tunable" because the micellar size can be easily adjusted by changing the pressure of CO(2). The microemulsion has potential applications in materials synthesis, chemical reactions, and extraction. PMID:21898733

  20. 1,2,3-triazolium ionic liquids

    SciTech Connect

    Luebke, David; Nulwala, Hunaid; Tang, Chau

    2014-12-09

    The present invention relates to compositions of matter that are ionic liquids, the compositions comprising substituted 1,2,3-triazolium cations combined with any anion. Compositions of the invention should be useful in the separation of gases and, perhaps, as catalysts for many reactions.

  1. Reactions of Starch in Ionic Liquids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We found that starches are found to be soluble at 80 ºC in ionic liquids such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-butyl-3-methylimidazolium dicyanamide (BMIMdca) in concentration up to 10% (w/w). Higher concentrations of biopolymers in these novel solvents resulted in solutions w...

  2. Esterification of Starch in Ionic Liquids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We shall discuss the use of various ionic liquids in the preparation of starch esters. Starch was reacted with vinyl acetate in different 1-butyl-3-methylimidazolium (bmim) salts as solvents in an effort to produce starches with different acetylation patterns. Overall degree of substitution (DS) w...

  3. Corneal storage at room temperature.

    PubMed

    Sachs, U; Goldman, K; Valenti, J; Kaufman, H E

    1978-06-01

    Short-term eye banking is based mainly on moist chamber and McCarey-Kaufman medium (M-K medium) preservation. Both involve a controlled 4 C temperature for storage. Warming the cornea to room temperature, however, drastically affects the endothelial viability. On enzymatic staining and histological study, the M-K medium-stored rabbit corneas had more normal endothelium than did "moist chamber" eyes when storage was prolonged for seven days at room temperature. In human corneas that were kept at 4 C for 24 hours and then exposed to a temperature of 25 C, destruction of organelles had occurred by six hours and was increased by 12 hours. Corneas that were kept in M-K medium had relatively intact endothelium after four days, but cell disruption and vacuolation was present by the seventh day. The M-K medium, therefore, affords protection to tissue warmed to room temperature, where metabolic activity is resumed. PMID:350203

  4. Application of Ionic Liquids in Amperometric Gas Sensors.

    PubMed

    Gębicki, Jacek; Kloskowski, Adam; Chrzanowski, Wojciech; Stepnowski, Piotr; Namiesnik, Jacek

    2016-01-01

    This article presents an analysis of available literature data on metrological parameters of the amperometric gas sensors containing ionic liquids as an electrolyte. Four mechanism types of signal generation in amperometric sensors with ionic liquid are described. Moreover, this article describes the influence of selected physico-chemical properties of the ionic liquids on the metrological parameters of these sensors. Some metrological parameters are also compared for amperometric sensors with GDE and SPE electrodes and with ionic liquids for selected analytes. PMID:25830724

  5. 'Liquid litmus': chemosensory pH-responsive photonic ionic liquids.

    PubMed

    Yung, Ka Yi; Schadock-Hewitt, Abby J; Hunter, Neil P; Bright, Frank V; Baker, Gary A

    2011-04-28

    We report on the founding member of a unique class of luminescent ionic liquids integrating a photoacidic anion that responds to the presence of both condensed- and gas-phase basicity; the analytical response is ratiometric in nature, visible to the naked eye, and offers fascinating prospects in smart photofluids, liquid logic gates, electronic noses, and sensory inks. PMID:21399813

  6. Room temperature terahertz polariton emitter

    SciTech Connect

    Geiser, Markus; Scalari, Giacomo; Castellano, Fabrizio; Beck, Mattias; Faist, Jerome

    2012-10-01

    Terahertz (THz) range electroluminescence from intersubband polariton states is observed in the ultra strong coupling regime, where the interaction energy between the collective excitation of a dense electron gas and a photonic mode is a significant portion of the uncoupled excitation energy. The polariton's increased emission efficiency along with a parabolic electron confinement potential allows operation up to room temperature in a nonresonant pumping scheme. This observation of room temperature electroluminescence of an intersubband device in the THz range is a promising proof of concept for more powerful THz sources.

  7. Electrochemistry of magnesium electrolytes in ionic liquids for secondary batteries.

    PubMed

    Vardar, Gulin; Sleightholme, Alice E S; Naruse, Junichi; Hiramatsu, Hidehiko; Siegel, Donald J; Monroe, Charles W

    2014-10-22

    The electrochemistry of Mg salts in room-temperature ionic liquids (ILs) was studied using plating/stripping voltammetry to assess the viability of IL solvents for applications in secondary Mg batteries. Borohydride (BH4(-)), trifluoromethanesulfonate (TfO(-)), and bis(trifluoromethanesulfonyl)imide (Tf2N(-)) salts of Mg were investigated. Three ILs were considered: l-n-butyl-3-methylimidazolium (BMIM)-Tf2N, N-methyl-N-propylpiperidinium (PP13)-Tf2N, and N,N-diethyl-N-methyl(2-methoxyethyl)ammonium (DEME(+)) tetrafluoroborate (BF4(-)). Salts and ILs were combined to produce binary solutions in which the anions were structurally similar or identical, if possible. Contrary to some prior reports, no salt/IL combination appeared to facilitate reversible Mg plating. In solutions containing BMIM(+), oxidative activity near 0.8 V vs Mg/Mg(2+) is likely associated with the BMIM cation, rather than Mg stripping. The absence of voltammetric signatures of Mg plating from ILs with Tf2N(-) and BF4(-) suggests that strong Mg/anion Coulombic attraction inhibits electrodeposition. Cosolvent additions to Mg(Tf2N)2/PP13-Tf2N were explored but did not result in enhanced plating/stripping activity. The results highlight the need for IL solvents or cosolvent systems that promote Mg(2+) dissociation. PMID:25248147

  8. Complex Capacitance Scaling in Ionic Liquids-filled Nanopores

    SciTech Connect

    Qiao, Rui; Huang, Jingsong; Meunier, Vincent; Sumpter, Bobby G; Peng, Wu

    2011-01-01

    Recent experiments have shown that the capacitance of sub-nanometer pores increases anomalously as the pore width decreases, thereby opening a new avenue for developing supercapacitors with enhanced energy density. However, this behavior is still subject to some controversy since its physical origins are not well understood. Using atomistic simulations, we show that the capacitance of slit-shaped nanopores in contact with room-temperature ionic liquids exhibits a U-shaped scaling behavior in pores with width from 0.75 to 1.26 nm. The left branch of the capacitance scaling curve directly corresponds to the anomalous capacitance increase and thus reproduces the experimental observations. The right branch of the curve indirectly agrees with experimental findings that so far have received little attention. The overall U-shaped scaling behavior provides insights on the origins of the difficulty in experimentally observing the pore-width dependent capacitance. We establish a theoretical framework for understanding the capacitance of electrical double layers in nanopores and provide mechanistic details into the origins of the observed scaling behavior. The framework highlights the critical role of ion solvation in controlling pore capacitance and the importance of choosing anion/cation couples carefully for optimal energy storage in a given pore system.

  9. Complex Capacitance Scaling in Ionic Liquids-Filled Nanopores

    SciTech Connect

    Sumpter, Bobby G

    2011-01-01

    Recent experiments have shown that the capacitance of subnanometer pores increases anomalously as the pore width decreases, thereby opening a new avenue for developing supercapacitors with enhanced energy density. However, this behavior is still subject to some controversy since its physical origins are not well understood. Using atomistic simulations, we show that the capacitance of slit-shaped nanopores in contact with room-temperature ionic liquids exhibits a U-shaped scaling behavior in pores with widths from 0.75 to 1.26 nm. The left branch of the capacitance scaling curve directly corresponds to the anomalous capacitance increase and thus reproduces the experimental observations. The right branch of the curve indirectly agrees with experimental findings that so far have received little attention. The overall U-shaped scaling behavior provides insights on the origins of the difficulty in experimentally observing the pore-width-dependent capacitance. We establish a theoretical framework for understanding the capacitance of electrical double layers in nanopores and provide mechanistic details into the origins of the observed scaling behavior. The framework highlights the critical role of 'ion solvation' in controlling pore capacitance and the importance of choosing anion/cation couples carefully for optimal energy storage in a given pore system.

  10. Distributed polarizability models for imidazolium-based ionic liquids.

    PubMed

    Millot, Claude; Chaumont, Alain; Engler, Etienne; Wipff, Georges

    2014-09-25

    Quantum chemical calculations are used to derive distributed polarizability models sufficiently accurate and compact to be used in classical molecular dynamics simulations of imidazolium-based room temperature ionic liquids. Two distributed polarizability models are fitted to reproduce the induction energy of three imidazolium cations (1,3-dimethyl-, 1-ethyl-3-methyl-, and 1-butyl-3-methylimidazolium) and four anions (tetrafluoroborate, hexafluorophosphate, nitrate, and thiocyanate) polarized by a point charge located successively on a grid of surrounding points. The first model includes charge-flow polarizabilities between first-neighbor atoms and isotropic dipolar polarizability on all atoms (except H), while the second model includes anisotropic dipolar polarizabilities on all atoms (except H). For the imidazolium cations, particular attention is given to the transferability of the distributed polarizability sets. The molecular polarizability and its anisotropy rebuilt by the distributed models are found to be in good agreement with the exact ab initio values for the three cations and 23 additional conformers of 1-ethyl-3-methyl-, 1-butyl-3-methyl-, 1-pentyl-3-methyl-, and 1-hexyl-3-methylimidazolium cations. PMID:25133873

  11. Molecular assembly-assisted biocatalytic reactions in ionic liquids.

    PubMed

    Moniruzzaman, Muhammad; Goto, Masahiro

    2011-01-01

    Room temperature ionic liquids (RTILs), having no measurable vapor pressure, represent an interesting class of tunable designer solvents. Due to their many unique properties, ILs have been used as attractive alternatives to environmentally harmful ordinary organic solvents in a wide range of applications including enzymatic biotransformation. Compared to conventional organic solvents, ILs offer many advantages for biocatalysis such as enhanced conversion rates, high enantioselectivity, better enzyme stability, and improved catalyst recoverability and recyclability. However, biocatalysis in ILs has not yet fully achieved its potential because many biocatalysts are insoluble in most ILs. This limitation could be overcome by the formation of nano/micrometer-sized aqueous microemulsion droplets in an IL continuous phase (referred to as water-in-IL microemulsions) stabilized by a layer of surfactants. Enzymes can be dissolved in such water droplets and protected from the unfavorable effect of ILs by the surfactant layer. In this chapter, a simple and effective method for the development of aqueous microemulsion droplets in a hydrophobic IL comprising an anionic surfactant sodium bis(2-ethyl-1-hexyl) sulfosuccinate (AOT) is presented. For this approach, we have synthesized a hydrophobic IL [C(8)mim][Tf(2)N] (1-octyl-3-methyl imidazolium bis(trifluoromethyl sulfonyl) amide) containing a long pendant hydrocarbon chain to facilitate the dissolution of AOT molecules. A detailed description of the procedure for the potential use of this newly developed water-in-IL reverse microemulsion for biocatalysis is also included. PMID:21553181

  12. Magnesium Battery Electrolytes in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Watkins, Tylan Strike

    A lack of adequate energy storage technologies is arguably the greatest hindrance to a modern sustainable energy infrastructure. Chemical energy storage, in the form of batteries, is an obvious solution to the problem. Unfortunately, today's state of the art battery technologies fail to meet the desired metrics for full scale electric grid and/or electric vehicle role out. Considerable effort from scientists and engineers has gone into the pursuit of battery chemistries theoretically capable of far outperforming leading technologies like Li-ion cells. For instance, an anode of the relatively abundant and cheap metal, magnesium, would boost the specific energy by over 4.6 times that of the current Li-ion anode (LiC6). The work presented here explores the compatibility of magnesium electrolytes in TFSI---based ionic liquids with a Mg anode (TFSI = bis(trifluoromethylsulfonyl)imide). Correlations are made between the Mg2+ speciation conditions in bulk solutions (as determined via Raman spectroscopy) and the corresponding electrochemical behavior of the electrolytes. It was found that by creating specific chelating conditions, with an appropriate Mg salt, the desired electrochemical behavior could be obtained, i.e. reversible electrodeposition and dissolution. Removal of TFSI -- contact ion pairs from the Mg2+ solvation shell was found to be essential for reversible electrodeposition. Ionic liquids with polyethylene glycol chains pendent from a parent pyrrolidinium cation were synthesized and used to create the necessary complexes with Mg 2+, from Mg(BH4)2, so that reversible electrodeposition from a purely ionic liquid medium was achieved. The following document discusses findings from several electrochemical experiments on magnesium electrolytes in ionic liquids. Explanations for the failure of many of these systems to produce reversible Mg electrodeposition are provided. The key characteristics of ionic liquid systems that are capable of achieving reversible Mg

  13. Ionic liquid containing hydroxamate and N-alkyl sulfamate ions

    DOEpatents

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

    2016-03-15

    Embodiments of the invention are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes a cation and an anion selected from hydroxamate and/or N-alkyl sulfamate anions.

  14. Synthesis of electroactive ionic liquids for flow battery applications

    SciTech Connect

    Anderson, Travis Mark; Ingersoll, David; Staiger, Chad; Pratt, Harry

    2015-09-01

    The present disclosure is directed to synthesizing metal ionic liquids with transition metal coordination cations, where such metal ionic liquids can be used in a flow battery. A cation of a metal ionic liquid includes a transition metal and a ligand coordinated to the transition metal.

  15. Synthesis and characterization of 1-(hydroxyethyl)-3-methylimidazolium sulfate and chloride ionic liquids

    NASA Astrophysics Data System (ADS)

    Chaker, Yassine; Ilikti, Hocine; Debdab, Mansour; Moumene, Taqiyeddine; Belarbi, El Habib; Wadouachi, Anne; Abbas, Ouissam; Khelifa, Brahim; Bresson, Serge

    2016-06-01

    We have used the imidazole as a starting compound for the preparation of a new ionic liquid 1-(hydroxyethyl)-3-methylimidazolium sulfate, with a yield of 98% in the two-steps synthesis. This new ionic liquid at room temperature exhibits a greater chemical activity. For the first step, we change the previous synthetic route using 2-chloroethanol as starting material, and with 1-methylimidazole to prepare the 1-(hydroxyethyl)-3-methylimidazolium chloride [EtOHMIM+][Cl-]. In the second stage, we have exchanged the anion Cl- with HSO4-. The ionic liquid shows reasonably high conductivity and thermal stability up to 340 °C. Our samples are characterized by 1H NMR, 13C NMR and FT-IR. The physical characteristics of the ionic liquid, such as solvation capacity were studied using a thermo-gravimetric Analyzer (NETZSCH DSC 204 F1) in the range of 40-400 °C. The results show that the ILs may be used as polyelectrolyte for electrochemical applications.

  16. Twin-peaks absorption spectra of excess electron in ionic liquids

    NASA Astrophysics Data System (ADS)

    Musat, Raluca M.; Kondoh, Takafumi; Yoshida, Yoichi; Takahashi, Kenji

    2014-07-01

    The solvated electron in room temperature ionic liquids (RTILs) has been the subject of several investigations and several reports exist on its nature and absorption spectrum. These studies concluded that the solvated electron exhibits an absorption spectrum peaking in the 1000-1400 nm region; a second absorption band peaking in the UV region has been assigned to the hole or dication radicals simultaneously formed in the system. Here we report on the fate of the excess electron in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, P14+/NTf2- using nanosecond pulse radiolysis. Scavenging experiments allowed us to record and disentangle the complex spectrum measured in P14+/NTf2-. We identified a bi-component absorption spectrum, due to the solvated electron, the absorption maxima located at 1080 nm and around 300 nm, as predicted by previous ab-initio molecular dynamics simulations for the dry excess electron. We also measured the spectra using different ionic liquids and confirmed the same feature of two absorption peaks. The present results have important implications for the characterization of solvated electrons in ionic liquids and better understanding of their structure and reactivity.

  17. Nanostructure of mixtures of protic ionic liquids and lithium salts: effect of alkyl chain length.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R; Cabeza, Óscar; Gallego, Luis J; Russina, Olga; Varela, Luis M

    2015-02-21

    The bulk structure of mixtures of two protic ionic liquids, propylammonium nitrate and butylammonium nitrate, with a salt with a common anion, is analyzed at room temperature by means of small angle X-ray scattering and classical molecular dynamics simulations. The study of several structural properties, such as density, radial distribution functions, spatial distribution functions, hydrogen bonds, coordination numbers and velocity autocorrelation functions, demonstrates that increasing the alkyl chain length of the alkylammonium cation results in more segregated, better defined polar and apolar domains, the latter having a larger size. This increase, ascribed to the erosion of the H-bond network in the ionic liquid polar regions as salt is added, is confirmed by means of small angle X-ray scattering measurements, which show a clear linear increase of the characteristic spatial sizes of the studied protic ionic liquids with salt concentration, similar to that previously reported for ethylammonium nitrate (J. Phys. Chem. B, 2014, 118, 761-770). In addition, larger ionic liquid cations lead to a lower degree of hydrogen bonding and to more sparsely packed three-dimensional structures, which are more easily perturbed by the addition of lithium salts. PMID:25609558

  18. Correlation of three-liquid-phase equilibria involving ionic liquids.

    PubMed

    Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A

    2016-08-01

    The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results. PMID:27427420

  19. Ionic liquids in refinery desulfurization: comparison between biphasic and supported ionic liquid phase suspension processes.

    PubMed

    Kuhlmann, Esther; Haumann, Marco; Jess, Andreas; Seeberger, Andreas; Wasserscheid, Peter

    2009-01-01

    The desulfurization of fuel compounds in the presence of ionic liquids is reported. For this purpose, the desulfurization efficiency of a variety of imidazolium phosphate ionic liquids has been tested. Dibenzothiophene/dodecane and butylmercaptan/decane mixtures were used as model systems. Single-stage extractions reduced the sulfur content from 500 ppm to 200 ppm. In multistage extractions the sulfur content could be lowered to less than 10 ppm within seven stages. Regeneration of the ionic liquid was achieved by distillation or re-extraction procedures. Supported ionic liquid phase (SILP) materials, obtained by dispersing the ionic liquid as a thin film on highly porous silica, exhibited a significantly higher extraction performance owing to their larger surface areas, reducing the sulfur content to less than 100 ppm in one stage. Multistage extraction with these SILP materials reduced the sulfur level to 50 ppm in the second stage. The SILP technology offers very efficient utilization of ionic liquids and circumvents mass transport limitations because of the small film thickness and large surface area, and allows application of the simple packed-bed column extraction technique. PMID:19798713

  20. Understanding the large solubility of lidocaine in 1-n-butyl-3-methylimidazolium based ionic liquids using molecular simulation

    NASA Astrophysics Data System (ADS)

    Ley, Ryan T.; Paluch, Andrew S.

    2016-02-01

    Room temperature ionic liquids have been proposed as replacement solvents in a wide range of industrial separation processes. Here, we focus on the use of ionic liquids as solvents for the pharmaceutical compound lidocaine. We show that the solubility of lidocaine in seven common 1-n-butyl-3-methylimidazolium based ionic liquids is greatly enhanced relative to water. The predicted solubility is greatest in [BMIM]+[CH3CO2]-, which we find results from favorable hydrogen bonding between the lidocaine amine hydrogen and the [CH3CO2]- oxygen, favorable electrostatic interactions between the lidocaine amide oxygen with the [BMIM]+ aromatic ring hydrogens, while lidocaine does not interfere with the association of [BMIM]+ with [CH3CO2]-. Additionally, by removing functional groups from the lidocaine scaffold while maintaining the important amide group, we found that as the van der Waals volume increases, solubility in [BMIM]+[CH3CO2]- relative to water increases.

  1. General impossibility to 'prescribe' diffusion for a geminate pair in a central force field and peculiarities of geminate in ionic liquids.

    SciTech Connect

    Shkrob, I. A.

    2011-05-12

    Given the difficulty of obtaining analytical solutions for the diffusion of interacting geminate pairs of (ion) radicals in liquids, it is common, following the original treatment of Mozumder, to 'prescribe' this diffusion. A demonstration is given that such a prescription is impossible for any interaction potential other than the Coulomb potential. This demonstration suggests the inadequacy of this common approach to modeling geminate pair and spur dynamics in the largest emerging class of organic solvents: room-temperature ionic liquids.

  2. Molecular dynamics simulation of imidazolium-based ionic liquids. II. Transport coefficients.

    PubMed

    Kowsari, M H; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

    2009-01-01

    A systematic molecular dynamics study is performed to determine the dynamics and transport properties of 12 room-temperature ionic liquids family with 1-alkyl-3-methylimidazolium cation, [amim](+) (alkyl = methyl, ethyl, propyl, and butyl), with counterions, PF(6)(-), NO(3)(-), and Cl(-). The goal of the work is to provide molecular level understanding of the transport coefficients of these liquids as guidance to experimentalists on choosing anion and cation pairs to match required properties of ionic liquid solvents. In the earlier paper (Part I), we characterized the dynamics of ionic liquids and provided a detailed comparison of the diffusion coefficients for each ion using the Einstein and Green-Kubo formulas. In this second part, other transport properties of imidazolium salts are calculated, in particular, the electrical conductivity is calculated from the Nernst-Einstein and Green-Kubo formulas. The viscosity is also determined from the Stokes-Einstein relation. The results of the calculated transport coefficients are consistent with the previous computational and experimental studies of imidazolium salts. Generally, the simulations give electrical conductivity lower than experiment while the viscosity estimate is higher than experiment. Within the same cation family, the ionic liquids with the NO(3)(-) counterion have the highest electrical conductivities: sigma[NO(3)](-)>sigma[PF(6)](-)>sigma[Cl](-). The [dmim][X] series, due to their symmetric cationic structure and good packing and the [bmim][X] series due to higher inductive van der Waals interactions of [bmim](+), have the highest viscosities in these ionic liquid series. Our simulations show that the major factors determining the magnitude of the self-diffusion, electrical conductivity, and viscosity are the geometric shape, ion size, and the delocalization of the ionic charge in the anion. PMID:19140627

  3. Active chemisorption sites in functionalized ionic liquids for carbon capture.

    PubMed

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

    Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined. PMID:27243042

  4. Phase behavior of ionic liquid crystals

    NASA Astrophysics Data System (ADS)

    Kondrat, S.; Bier, M.; Harnau, L.

    2010-05-01

    Bulk properties of ionic liquid crystals are investigated using density functional theory. The liquid crystal molecules are represented by ellipsoidal particles with charges located in their center or at their tails. Attractive interactions are taken into account in terms of the Gay-Berne pair potential. Rich phase diagrams involving vapor, isotropic and nematic liquid, as well as smectic phases are found. The dependence of the phase behavior on various parameters such as the length of the particles and the location of charges on the particles is studied.

  5. Triphenylene-Based Room-Temperature Discotic Liquid Crystals: A New Class of Blue-Light-Emitting Materials with Long-Range Columnar Self-Assembly.

    PubMed

    Gupta, Monika; Pal, Santanu Kumar

    2016-02-01

    A straightforward synthesis of multialkynylbenzene-bridged triphenylene-based dyad systems (via flexible alkyl spacers) that self-organize into room-temperature columnar structures over a long range is reported. The compounds with spacer lengths (n) of 8 and 10 exhibit a columnar rectangular mesophase whereas a compound with n = 6 shows a columnar rectangular plastic phase. Interestingly, the later compound (n = 6) shows the formation of well-nucleated spherulites of about several hundred micrometers that suggest the existence of a long-range uniform self-assembly of columns. All of these compounds show blue luminescence in solution and in the thin-film state under long-wavelength (365 nm) UV light. These compounds fulfill the described demands such as long-range columnar self-assembly at room temperature, a good yield with high purity, and blue-light emitters under the neat condition for possible potential applications in semiconductor devices. They also match the criteria of facile processing from the isotropic state because of their low isotropization temperature. This new class of materials is promising, considering the emissive nature and stabilization of the columnar mesophase at ambient temperature. PMID:26745267

  6. Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

    PubMed

    Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

    2016-01-14

    In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested. PMID:26661060

  7. Adsorption of ionic liquid onto halloysite nanotubes: Thermal and mechanical properties of heterophasic PE-PP copolymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Bischoff, E.; Simon, D. A.; Liberman, S. A.; Mauler, R. S.

    2016-03-01

    The surface adsorption of inorganic clays with ionic liquids has attracted much attention due to improve the interaction of hydrophilic clay with the hydrophobic polymers. However, successful organic adsorption strongly depends on the characteristics of ionic liquid (anion, chain size and concentration), and the reaction conditions (as polarity of solvent). In this study, such factors were analyzed and correlated with morphology, thermal and mechanical properties of the nanocomposites. The heterophasic ethylene-propylene copolymer nanocomposites were prepared by melt intercalation method in a twin screw co-rotating extruder. The halloysite nanotubes (HNT) was used as filler - natural and modified with different ionic liquids. The results showed that a better distribution and dispersion of the nanoparticles was achieved in the samples with modified HNT (m-HNT) and was more significant when the ionic liquid adsorption was conducted in a less polar solvent. The thermal stability of the nanocomposites with m- HNT was higher compared to the neat CP. Additionally, the better balance in the mechanical properties was obtained by the use of the more hydrophobic ionic liquid and higher concentration with improve of 27% in the Young Modulus without loss in the impact properties at room temperature. These superior behaviors of ionic liquid adsorption products exhibit properties suitable for many industrial applications.

  8. Ionic liquids as surfactants in micellar liquid chromatography.

    PubMed

    Flieger, Jolanta; Siwek, Agata; Pizoń, Magdalena; Czajkowska-Żelazko, Anna

    2013-05-01

    This paper is devoted to application of ionic liquids as surfactants in LC of organic compounds, derivatives of 1,4-thiosemicarbazides. According to HPLC requirements the most advantageous conditions such as transparency for ultraviolet light, low CMC, additional inorganic salt additives, and appropriate organic solvent were established. The CMC was determined using conductivity measurements. Suitability of two different stationary phases: RP-C18 and cyanopropyl bonded phase was examined under micellar conditions. Chosen ionic liquid surfactant was compared to common traditional amphiphilic reagent - SDS. Elaborated on chromatographic micellar conditions were tested as a pilot technique for prediction of distribution coefficients of organic analytes in ionic liquid-based aqueous two-phase system. PMID:23609988

  9. Interactions in ion pairs of protic ionic liquids: Comparison with aprotic ionic liquids

    SciTech Connect

    Tsuzuki, Seiji; Shinoda, Wataru; Miran, Md. Shah; Kinoshita, Hiroshi; Yasuda, Tomohiro; Watanabe, Masayoshi

    2013-11-07

    The stabilization energies for the formation (E{sub form}) of 11 ion pairs of protic and aprotic ionic liquids were studied by MP2/6-311G{sup **} level ab initio calculations to elucidate the difference between the interactions of ions in protic ionic liquids and those in aprotic ionic liquids. The interactions in the ion pairs of protic ionic liquids (diethylmethylammonium [dema] and dimethylpropylammonium [dmpa] based ionic liquids) are stronger than those of aprotic ionic liquids (ethyltrimethylammonium [etma] based ionic liquids). The E{sub form} for the [dema][CF{sub 3}SO{sub 3}] and [dmpa][CF{sub 3}SO{sub 3}] complexes (−95.6 and −96.4 kcal/mol, respectively) are significantly larger (more negative) than that for the [etma][CF{sub 3}SO{sub 3}] complex (−81.0 kcal/mol). The same trend was observed for the calculations of ion pairs of the three cations with the Cl{sup −}, BF{sub 4}{sup −}, TFSA{sup −} anions. The anion has contact with the N–H bond of the dema{sup +} or dmpa{sup +} cations in the most stable geometries of the dema{sup +} and dmpa{sup +} complexes. The optimized geometries, in which the anions locate on the counter side of the cations, are 11.0–18.0 kcal/mol less stable, which shows that the interactions in the ions pairs of protic ionic liquids have strong directionality. The E{sub form} for the less stable geometries for the dema{sup +} and dmpa{sup +} complexes are close to those for the most stable etma{sup +} complexes. The electrostatic interaction, which is the major source of the attraction in the ion pairs, is responsible for the directionality of the interactions and determining the magnitude of the interaction energy. Molecular dynamic simulations of the [dema][TFSA] and [dmpa][TFSA] ionic liquids show that the N–H bonds of the cations have contact with the negatively charged (oxygen and nitrogen) atoms of TFSA{sup −} anion, while the strong directionality of the interactions was not suggested from the simulation

  10. Application of ionic liquids containing tricyanomethanide [C(CN)3]- or tetracyanoborate [B(CN)4]- anions in dye-sensitized solar cells.

    PubMed

    Marszalek, Magdalena; Fei, Zhaofu; Zhu, Dun-Ru; Scopelliti, Rosario; Dyson, Paul J; Zakeeruddin, Shaik Mohammed; Grätzel, Michael

    2011-11-21

    A series of novel ionic liquids composed of imidazolium, pyridinium, pyrrolidinium, and ammonium cations with tricyanomethanide or tetracyanoborate anions were prepared. The ionic liquids were characterized by NMR and IR spectroscopy and ESI-mass spectrometry, and their physical properties were investigated. Solid state structures of the N-propyl-N-methylpyrrolidinium and triethylpropylammonium tetracyanoborate salts were obtained by single crystal X-ray diffraction. The salts that are liquid at room temperature were evaluated as electrolyte additives in dye-sensitized solar cells, giving rise to efficiencies 7.35 and 7.85% under 100 and 10% Sun, respectively, in combination with the standard Z907 dye. PMID:22026738

  11. Structural and Aggregation Study of Protic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Mattedi, S.; Martin-Pastor, M.; Iglesias, M.

    2011-12-01

    In this work there were studied structural and agreggation aspects of ionic liquids formed by the reaction between ethanolamines with low chain organic acids using NMR techniques. Three ionic liquids composed of pentanoic acid and (mono-, di- and tri-) ethanol amine were studied by 1H, and 13C solution NMR methods. NMR assisted the chemical and quantitative characterization of these three ionic liquids and provided insight in their structural arrangement of their components in the ionic liquid medium. The obtained results could be used to understand the structure and aggregation pattern of these ionic liquids and helps in the development of possible industrial applications.

  12. Increasing the intensity of protonated secondary ions in time-of-flight secondary ion mass spectrometry using a proton-conducting ionic liquid, diethylmethylammonium trifluoromethanesulfonate

    NASA Astrophysics Data System (ADS)

    Fujiwara, Yukio; Saito, Naoaki

    2015-07-01

    To increase the secondary ion intensities of organic molecules, room-temperature ionic liquids were investigated in two time-of-flight secondary ion mass spectrometry (TOF-SIMS) experiments. First, ionic liquids as well as glycerol were tested as liquid matrices of arginine. The secondary ion intensity of protonated arginine was increased 200-fold by using a proton-conducting ionic liquid, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]). The matrix effect of [dema][TfO] was higher than that of glycerol, which is a typical matrix in SIMS. Next, ionic liquids were tested as primary ion beams. The number of protonated secondary ions of arginine was significantly increased by using a primary ion beam of [dema][TfO].

  13. Sodium-ion electrolytes based on ionic liquids: a role of cation-anion hydrogen bonding.

    PubMed

    Chaban, Vitaly V; Andreeva, Nadezhda A

    2016-08-01

    Recent success of the sodium-ion batteries fosters an academic interest for their investigation. Room-temperature ionic liquids (RTILs) constitute universal solvents providing non-volatility and non-flammability to electrolytes. In the present work, we consider four families of RTILs as prospective solvents for NaBF4 and NaNO3 with an inorganic salt concentration of 25 and 50 mol%. We propose a methodology to rate RTILs according to their solvation capability using parameters of the computed radial distribution functions. Hydrogen bonds between the cations and the anions of RTILs were found to indirectly favor sodium solvation, irrespective of the particular RTIL and its concentration. The best performance was recorded in the case of cholinium nitrate. The reported observations and correlations of ionic structures and properties offer important assistance to an emerging field of sodium-ion batteries. Graphical Abstract Sodium-ion electrolytes. PMID:27381471

  14. Checkerboard Self-Patterning of an Ionic Liquid Film on Mercury

    SciTech Connect

    L Tamam; B Ocko; H Reichert; M Deutsch

    2011-12-31

    {angstrom}-resolution studies of room temperature ionic liquid (RTIL) interfaces are scarce, in spite of their long-recognized importance for the science and many applications of RTILs. We present an {angstrom}-resolution x-ray study of a Langmuir film of an RTIL on mercury. At low (high) coverage [90 (50) {angstrom}{sup 2}/molecule] a mono-(bi)layer of surface-parallel molecules is found. The molecules self-assemble in a lateral ionic checkerboard pattern, unlike the uniform-charge, alternate-ion layers of this RTIL at its bulk-solid interface. A 2D-smectic order is found, with molecules packed in parallel stripes, forming long-range order normal to, but none along, the stripes.

  15. Checkerboard Self-Patterning of an Ionic Liquid Film on Mercury

    SciTech Connect

    Ocko, B.M.; Tamam, L.; Reichert, H.; Deutsch, M.

    2011-05-10

    {angstrom}-resolution studies of room temperature ionic liquid (RTIL) interfaces are scarce, in spite of their long-recognized importance for the science and many applications of RTILs. We present an {angstrom}-resolution x-ray study of a Langmuir film of an RTIL on mercury. At low (high) coverage [90 (50) {angstrom}{sup 2}/molecule] a mono-(bi)layer of surface-parallel molecules is found. The molecules self-assemble in a lateral ionic checkerboard pattern, unlike the uniform-charge, alternate-ion layers of this RTIL at its bulk-solid interface. A 2D-smectic order is found, with molecules packed in parallel stripes, forming long-range order normal to, but none along, the stripes.

  16. Reversible Hydrophobic-Hydrophilic Transition of Ionic Liquids Driven by Carbon Dioxide.

    PubMed

    Xiong, Dazhen; Cui, Guokai; Wang, Jianji; Wang, Huiyong; Li, Zhiyong; Yao, Kaisheng; Zhang, Suojiang

    2015-06-15

    Ionic liquids (ILs) with a reversible hydrophobic-hydrophilic transition were developed, and they exhibited unique phase behavior with H2O: monophase in the presence of CO2, but biphase upon removal of CO2 at room temperature and atmospheric pressure. Thus, coupling of reaction, separation, and recovery steps in sustainable chemical processes could be realized by a reversible liquid-liquid phase transition of such IL-H2O mixtures. Spectroscopic investigations and DFT calculations showed that the mechanism behind hydrophobic-hydrophilic transition involved reversible reaction of CO2 with anion of the ILs and formation of hydrophilic ammonium salts. These unique IL-H2O systems were successfully utilized for facile one-step synthesis of Au porous films by bubbling CO2 under ambient conditions. The Au porous films and the ILs were then separated simultaneously from aqueous solutions by bubbling N2, and recovered ILs could be directly reused in the next process. PMID:25925191

  17. Conductivity Scaling Relationships in Nanostructured Membranes based on Protic Polymerized Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Lynd, Nathaniel; Segalman, Rachel

    2015-03-01

    Nanostructured membranes based on protic polymerized ionic liquids are of great interest for a variety of electrochemical applications. Understanding the relationship between composition, structure, and ionic conductivity for these materials is essential for designing novel membranes with improved properties. In this work, we explore the effect of volume fraction of ionic liquid on conductivity, σ using a model system composed of poly[isoprene-block-(ethylene oxide-stat-histamine glycidyl ether) diblock copolymers [PI- b - P(EO-stat-HGE)] and the resulting [PI- b - P(EO-stat-IL)] obtained after treatment with trifluoroacetic acid. These materials self-assemble into lamellar structures with volume fractions of ionic liquid ranging from 0.50 to 0.90 as demonstrated by SAXS. PI- b - P(EO-stat-IL) membranes exhibit conductivities up to 4 x 10-3 S/cm at room temperature. In addition, PI- b - P(EO-stat-IL) based membranes have lower water uptake (λ = 8-10) in comparison with most proton conducting membranes reported elsewhere. The low λ in these membranes might translate into a stronger effect of morphology on transport properties. Joint Center for Artificial Photosynthesis.

  18. [Advances of poly (ionic liquid) materials in separation science].

    PubMed

    Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

    2015-11-01

    Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials. PMID:26939357

  19. Dynamics of Ion Transport in Ionic Liquids.

    PubMed

    Lee, Alpha A; Kondrat, Svyatoslav; Vella, Dominic; Goriely, Alain

    2015-09-01

    A gap in understanding the link between continuum theories of ion transport in ionic liquids and the underlying microscopic dynamics has hindered the development of frameworks for transport phenomena in these concentrated electrolytes. Here, we construct a continuum theory for ion transport in ionic liquids by coarse graining a simple exclusion process of interacting particles on a lattice. The resulting dynamical equations can be written as a gradient flow with a mobility matrix that vanishes at high densities. This form of the mobility matrix gives rise to a charging behavior that is different to the one known for electrolytic solutions, but which agrees qualitatively with the phenomenology observed in experiments and simulations. PMID:26382685

  20. Dissolution enthalpies of cellulose in ionic liquids.

    PubMed

    Parviainen, Helena; Parviainen, Arno; Virtanen, Tommi; Kilpeläinen, Ilkka; Ahvenainen, Patrik; Serimaa, Ritva; Grönqvist, Stina; Maloney, Thaddeus; Maunu, Sirkka Liisa

    2014-11-26

    In this work, interactions between cellulose and ionic liquids were studied calorimetrically and by optical microscopy. Two novel ionic liquids (1,5-Diazabicyclo[4.3.0]non-5-enium propionate and N-methyl-1,5-diazabicyclo[4.3.0]non-5-enium dimethyl phosphate) and 1-ethyl-3-methylimidazolium acetate-water mixtures were used as solvents. Optical microscopy served in finding the extent of dissolution and identifying the dissolution pattern of the cellulose sample. Calorimetric studies identified a peak relating to dissolution of cellulose in solvent. The transition did, however, not indicate complete dissolution, but rather dissolution inside fibre or fibrils. This method was used to study differences between four cellulose samples with different pretreatment or origins. PMID:25256460

  1. Furfural production using ionic liquids: A review.

    PubMed

    Peleteiro, Susana; Rivas, Sandra; Alonso, José Luis; Santos, Valentín; Parajó, Juan Carlos

    2016-02-01

    Furfural, a platform chemical with a bright future, is commercially obtained by acidic processing of xylan-containing biomass in aqueous media. Ionic liquids (ILs) can be employed in processed for furfural manufacture as additives, as catalysts and/or as reaction media. Depending on the IL utilized, externally added catalysts (usually, Lewis acids, Brönsted acids and/or solid acid catalysts) can be necessary to achieve high reaction yields. Oppositely, acidic ionic liquids (AILs) can perform as both solvents and catalysts, enabling the direct conversion of suitable substrates (pentoses, pentosans or xylan-containing biomass) into furfural. Operating in IL-containing media, the furfural yields can be improved when the product is continuously removed along the reaction (for example, by stripping or extraction), to avoid unwanted side-reactions leading to furfural consumption. These topics are reviewed, as well as the major challenges involved in the large scale utilization of ILs for furfural production. PMID:26708486

  2. Nontoxic Ionic Liquid Fuels for Exploration Applications

    NASA Technical Reports Server (NTRS)

    Coil, Millicent

    2015-01-01

    The toxicity of propellants used in conventional propulsion systems increases not only safety risks to personnel but also costs, due to special handling required during the entire lifetime of the propellants. Orbital Technologies Corporation (ORBITEC) has developed and tested novel nontoxic ionic liquid fuels for propulsion applications. In Phase I of the project, the company demonstrated the feasibility of several ionic liquid formulations that equaled the performance of conventional rocket propellant monomethylhydrazine (MMH) and also provided low volatility and low toxicity. In Phase II, ORBITEC refined the formulations, conducted material property tests, and investigated combustion behavior in droplet and microreactor experiments. The company also explored the effect of injector design on performance and demonstrated the fuels in a small-scale thruster. The ultimate goal is to replace propellants such as MMH with fuels that are simultaneously high-performance and nontoxic. The fuels will have uses in NASA's propulsion applications and also in a range of military and commercial functions.

  3. A preconcentration method for analysis of neonicotinoids in honey samples by ionic liquid-based cold-induced aggregation microextraction.

    PubMed

    Vichapong, Jitlada; Burakham, Rodjana; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

    2016-08-01

    A preconcentration approach based on ionic liquid-based cold-induced aggregation microextraction for determination of neonicotinoid insecticide residues in honey samples before high-performance liquid chromatographic analysis has been developed. Room temperature ionic liquid [C4MIM][PF6] (extraction solvent) and SDS (emulsifier) was used for extraction of the target analytes. The parameters affecting the extraction efficiency were optimized. The optimum microextraction conditions were 200µL room temperature ionic liquids [C4MIM][PF6] containing 0.05molL(-1) SDS, 0.75g sodium carbonate, vortex agitation speed of 1800rpm for 30s and centrifugation at 3500rpm for 10min. Under optimum conditions, the high enrichment factors of 200 could be obtained, leading to low limit of detection (0.01µgL(-1) for all analytes) with the relative standard deviations lower than 2.68% and 5.38% for retention time and peak area, respectively. Good recoveries for the spiked target neonicotinoids at three different concentrations of honey samples were obtained in 86-100% and relative standard deviations were lower than 8.1%. The results demonstrated that the proposed method can be used as an alternative powerful method for the simultaneous determination of the studied insecticides in real honey samples. PMID:27216676

  4. Structural modifications of nucleosides in ionic liquids

    PubMed Central

    Kumar, Vineet; Parmar, Virinder S.; Malhotra, Sanjay V.

    2011-01-01

    Nucleoside chemistry represents an important research area for drug discovery, as many nucleoside analogs are prominent drugs and have been widely applied for cancer and viral chemotherapy. However, the synthesis of modified nucleosides presents a major challenge, which is further aggravated by poor solubility of these compounds in common organic solvents. Most of the currently available methods for nucleoside modification employ toxic high boiling solvents; require long reaction time and tedious workup methods. As such, there is constant effort to develop process chemistry in alternative medium to limit the use of organic solvents that are hazardous to the environment and can be deleterious to human health. One such approach is to use ionic liquids, which are ‘designer materials’ with unique and tunable physico-chemical properties. Studies have shown that methodologies using ionic liquids are highly efficient and convenient for the synthesis of nucleoside analogs, as demonstrated by the preparation of pharmaceutically important anti-viral drugs. This article summarizes recent efforts on nucleoside modification using ionic liquids. PMID:20178825

  5. Understanding SO2 Capture by Ionic Liquids.

    PubMed

    Mondal, Anirban; Balasubramanian, Sundaram

    2016-05-19

    Ionic liquids have generated interest for efficient SO2 absorption due to their low vapor pressure and versatility. In this work, a systematic investigation of the structure, thermodynamics, and dynamics of SO2 absorption by ionic liquids has been carried out through quantum chemical calculations and molecular dynamics (MD) simulations. MP2 level calculations of several ion pairs complexed with SO2 reveal its preferential interaction with the anion. Results of condensed phase MD simulations of SO2-IL mixtures manifested the essential role of both cations and anions in the solvation of SO2, where the solute is surrounded by the "cage" formed by the cations (primarily its alkyl tail) through dispersion interactions. These structural effects of gas absorption are substantiated by calculated Gibbs free energy of solvation; the dissolution is demonstrated to be enthalpy driven. The entropic loss of SO2 absorption in ionic liquids with a larger anion such as [NTf2](-) has been quantified and has been attributed to the conformational restriction of the anion imposed by its interaction with SO2. SO2 loading IL decreases its shear viscosity and enhances the electrical conductivity. This systematic study provides a molecular level understanding which can aid the design of task-specific ILs as electrolytes for efficient SO2 absorption. PMID:27119562

  6. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air

    PubMed Central

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-01-01

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection. PMID:27070588

  7. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air.

    PubMed

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-01-01

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m²/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection. PMID:27070588

  8. Effect of pyrrolidinium based ionic liquid on the channel form of gramicidin in lipid vesicles.

    PubMed

    Singh, Upendra Kumar; Dohare, Neeraj; Mishra, Prabhash; Singh, Prashant; Bohidar, Himadri B; Patel, Rajan

    2015-08-01

    The present work is focused on the interaction between membrane bound gramicidin and 1-butyl-1-methyl-2-oxopyrrolidinium bromide (BMOP) ionic liquid. Ionic liquids (ILs) are solvents that are often liquid at room temperature and composed of organic cation and appropriate anion. The gramicidin peptide forms prototypical ion channels for cations, which have been extensively used to study the organization, dynamics, and function of membrane spanning channels. The interaction was studied by circular dichroism, steady state, time-resolved fluorescence spectroscopy in combination with dynamic surface tension and field emission scanning electron microscopic methods (FESEM). The results obtained from circular dichroism shows that the BMOP interacts with the channel form of gramicidin in lipid vesicle without any considerable effect on its conformation. The Red-edge excitation shift (REES) also supported the above findings. In addition, the fluorescence studies suggested that BMOP makes ground state complex with ion channel, which was further supported by time resolved measurements. Furthermore, dynamic surface tension analysis shows the faster adsorption of BMOP with membrane bound gramicidin at the air-water interface. Additionally, FESEM results indicated that BMOP forms a film around the membrane bound gramicidin at higher concentration. These results are potentially useful to analyze the effect of ionic liquids on the behaviour of membrane proteins. PMID:26025771

  9. Synthesis and anti-microbial potencies of 1-(2-hydroxyethyl)-3-alkylimidazolium chloride ionic liquids: microbial viabilities at different ionic liquids concentrations.

    PubMed

    Hossain, M Ismail; El-Harbawi, Mohanad; Alitheen, Noorjahan Banu Mohamed; Noaman, Yousr Abdulhadi; Lévêque, Jean-Marc; Yin, Chun-Yang

    2013-01-01

    Three 1-(2-hydroxyethyl)-3-alkylimidazolium chloride room temperature ionic liquids (ILs) [2OHimC(n)][Cl]; (n=0, 1, 4) have been synthesized from the appropriate imidazole precursors and characterized by IR and NMR spectroscopies and elemental analysis. Their anti-microbial activities were investigated using the well-diffusion method. The viabilities of Escherichia coli, Aeromonas hydrophila, Listeria monocytogenes and Salmonella enterica as a function of IL concentrations were studied. The minimal inhibitory concentrations (MICs) and EC₅₀ values for the present ILs were within the concentration range from 60 to 125 mM and 23 to 73 mM. The anti-microbial potencies of the present ILs were compared to a standard antibiotic, gentamicin. The finding affords additional perspective on the level of ILs toxicity to aquatic lifeforms and yet, this characteristic can be readily harnessed to detect microbial growth and activity. PMID:23107478

  10. Biocompatible ionic liquids: a new approach for stabilizing proteins in liquid formulation.

    PubMed

    Vrikkis, Regina M; Fraser, Kevin J; Fujita, Kyoko; Macfarlane, Douglas R; Elliott, Gloria D

    2009-07-01

    Ionic liquids (ILs) have shown excellent promise as both solutes and solvents for stabilizing proteins at room temperature. Because many modern drugs are protein-based, these stabilizing characteristics have great potential to provide advances in the field of liquid formulation of therapeutic proteins. However, before these developments can be translated into clinical solutions it is essential to establish data related to the biocompatibility of these ILs. The current work investigates the cytotoxicity of several ILs that were rationally synthesized from natural biomolecules and compounds that have already been approved as excipients for drug formulations. The effect of choline dihydrogen phosphate (choline dhp), choline saccharinate, and 1-butyl 3-methyl imidazolium lactate (bmim lactate) on the metabolic activity of a mouse macrophage cell line (J774) was assessed using the reduction in resazurin as an indicator of activity and, by extension, viability. Two formulations of lysozyme (10 mg/ml and 100 mg/ml) in 80 wt % choline dhp (aq) were prepared and the proteins were evaluated for structural stability immediately following formulation and again at 1 month. Equivalent formulations in 0.1 M Na acetate aqueous buffer were evaluated as controls. A differential scanning microcalorimeter (DSC) was used to evaluate the structural stability on the basis of the unfolding temperature and the enthalpy of unfolding, and a micrococcus lysodiekticus activity test was used to evaluate functional activity. All compounds were found to be relatively benign, with toxicity increasing in the order choline dhpionic liquids. PMID:19640150

  11. Novel room temperature ferromagnetic semiconductors

    SciTech Connect

    Gupta, Amita

    2004-11-01

    Today's information world, bits of data are processed by semiconductor chips, and stored in the magnetic disk drives. But tomorrow's information technology may see magnetism (spin) and semiconductivity (charge) combined in one 'spintronic' device that exploits both charge and 'spin' to carry data (the best of two worlds). Spintronic devices such as spin valve transistors, spin light emitting diodes, non-volatile memory, logic devices, optical isolators and ultra-fast optical switches are some of the areas of interest for introducing the ferromagnetic properties at room temperature in a semiconductor to make it multifunctional. The potential advantages of such spintronic devices will be higher speed, greater efficiency, and better stability at a reduced power consumption. This Thesis contains two main topics: In-depth understanding of magnetism in Mn doped ZnO, and our search and identification of at least six new above room temperature ferromagnetic semiconductors. Both complex doped ZnO based new materials, as well as a number of nonoxides like phosphides, and sulfides suitably doped with Mn or Cu are shown to give rise to ferromagnetism above room temperature. Some of the highlights of this work are discovery of room temperature ferromagnetism in: (1) ZnO:Mn (paper in Nature Materials, Oct issue, 2003); (2) ZnO doped with Cu (containing no magnetic elements in it); (3) GaP doped with Cu (again containing no magnetic elements in it); (4) Enhancement of Magnetization by Cu co-doping in ZnO:Mn; (5) CdS doped with Mn, and a few others not reported in this thesis. We discuss in detail the first observation of ferromagnetism above room temperature in the form of powder, bulk pellets, in 2-3 mu-m thick transparent pulsed laser deposited films of the Mn (<4 at. percent) doped ZnO. High-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) spectra recorded from 2 to 200nm areas showed homogeneous distribution of Mn substituting

  12. Lysozyme Solubility and Conformation in Neat Ionic Liquids and Their Mixtures with Water.

    PubMed

    Strassburg, Stephen; Bermudez, Harry; Hoagland, David

    2016-06-13

    The room temperature solubility of a number of model proteins is assessed for a diverse set of neat ionic liquids (ILs). For two soluble protein-IL pairs, lysozyme in [C2MIM][EtSO4] (1-ethyl-3-methylimidazolium ethylsulfate) and in [C2,4,4,4P][Et2PO4] (tributyl(ethyl)phosphonium diethylphosphate), protein solubility and structure at various temperatures are probed by dynamic light scattering (assessing dissolved molecular size), turbidimetry (reflecting degree of solubility), and Fourier transform infrared spectroscopy (uncovering helical secondary structure). As compared to aqueous environments, [C2,4,4,4P][Et2PO4] thermally stabilizes protein size and secondary structure while [C2MIM][EtSO4] does the opposite. Lysozyme denatured in [C2MIM][EtSO4] does not aggregate, presumably due to an absence of hydrophobic interactions, and the denaturation appears thermally reversible. Both ILs at room temperature are miscible with water in all proportions, but to create the corresponding ternary mixtures with protein, the order of mixing is important. Mixed to avoid additions of water to IL-dissolved protein, stable solutions are obtained with [C2MIM][EtSO4] at all solvent compositions. When water is added to IL-rich solutions, liquid-liquid demixing is noted. PMID:27159556

  13. Ionic liquid based multifunctional double network gel

    NASA Astrophysics Data System (ADS)

    Ahmed, Kumkum; Higashihara, Tomoya; Arafune, Hiroyuki; Kamijo, Toshio; Morinaga, Takashi; Sato, Takaya; Furukawa, Hidemitsu

    2015-04-01

    Gels are a promising class of soft and wet materials with diverse application in tissue engineering and bio-medical purpose. In order to accelerate the development of gels, it is required to synthesize multi-functional gels of high mechanical strength, ultra low surface friction and suitable elastic modulus with a variety of methods and new materials. Among many types of gel ionic gel made from ionic liquids (ILs) could be used for diverse applications in electrochemical devices and in the field of tribology. IL, a promising materials for lubrication, is a salt with a melting point lower than 100 °C. As a lubricant, ILs are characterized by an extremely low vapor pressure, high thermal stability and high ion conductivity. In this work a novel approach of making double network DN ionic gel using IL has been made utilizing photo polymerization process. A hydrophobic monomer Methyl methacrylate (MMA) has been used as a first network and a hydrophobic IL monomer, N,N-diethyl-N-(2-mthacryloylethyl)-N-methylammonium bistrifluoromethylsulfonyl)imide (DEMM-TFSI) has been used as a second network using photo initiator benzophenon and crosslinker triethylene glycol dimethacrylate (TEGDMA). The resulting DN ionic gel shows transparency, flexibility, high thermal stability, good mechanical toughness and low friction coefficient value which can be a potential candidate as a gel slider in different mechanical devices and can open a new area in the field of gel tribology.

  14. Room temperature electrodeposition of molybdenum sulfide for catalytic and photoluminescence applications.

    PubMed

    Murugesan, Sankaran; Akkineni, Arunkumar; Chou, Brendan P; Glaz, Micah S; Vanden Bout, David A; Stevenson, Keith J

    2013-09-24

    An elegant method for the electrodeposition of MoS2 thin films using room temperature ionic liquids (RTIL) as an electrolyte was developed. Simple molecular precursors of Mo and S were added in different concentrations to tune the composition and deposition process. The electrodeposition of MoS2 was confirmed with both Raman spectroscopy and XPS. Analysis showed that the electrodeposited MoS2 films form a flower shape morphology with edge active sites that promote the hydrogen evolution reaction (HER). Furthermore, this technique enables selective tuning of the film thickness and demonstrates high photoluminescence activity with a decrease in the number of layers. PMID:23962095

  15. [Determination of oleanic acid and paeoniflorin in Paeonia lactiflora by ultrasound-assisted ionic liquid-reversed phase liquid chromatography].

    PubMed

    Liu, Wei; Li, Dong-dong; Yang, Hong-shuai; Chen, Yuan-yuan; Wei, Jin-feng; Kang, Wen-yi; Guo, Xiu-chun

    2015-02-01

    Four kinds of ionic liquids [BMIM] Br, [BMIM] BF4, [BMIM] PF6, [HMIM] PF6 were used to analyze the content of oleanic acid and paeoniflorin in Paeonia lactiflora with ultrasonic-assisted extraction coupled with HPLC. The chromatographic column, Purospher star RP-C18 (4.6 mm x 250 mm, 5 μm), was used. Acetonitrile and water (90:10) as mobile phase was used to determine the content of oleanic acid with a gradient elution and flow rate at 1.00 mL · min(-1), detection wavelength at 210 nm, chromatographic column temperature at room temperature. Paeoniflorin content was determined using acetonitrile and water (18:82) as mobile phase with a gradient elution and flow rate at 1.00 mL · min(-1), detection wavelength at 250 nm, the chromatographic column temperature at room temperature. The result show that oleanic acid has the highest extraction yield when the conditions are solid-liquid ratio of 1:80 (g · mL(-1)), and the [BMIM] Br methanol solution concentration of 0.6 mol · L(-1). Under the optimal extraction conditions, the content of oleanic acid from 0.24 to 3.76 μg showed a good linearity (r = 0.9999), the average recovery was 97.20%. Paeoniflorin has the highest extraction yield when the conditions are solid-liquid ratio of 1:130 (g · mL(-1)), and the [C4 MIM] PF6 methanol solution concentration of 0.6 mol · L(-1). Under the optimal extraction conditions, paeoniflorin content from 0.42 to 4.20 μg showed a good lin- earity (r = 1.000), the average recovery was 98.84%. This method is simple and reliable, its repeatability is also very good. It has important significance in the study P. lactiflora of ionic liquid microextraction. PMID:26084167

  16. A new QM/MM method oriented to the study of ionic liquids.

    PubMed

    Sánchez, M Luz; Corchado, José C; Martín, M Elena; Galván, Ignacio Fdez; Barata-Morgado, Rute; Aguilar, Manuel A

    2015-09-30

    The interest on room temperature ionic liquids has grown in the last decades because of their use as all-purpose solvent and their low environmental impact. In the present work, a new theoretical procedure is developed to study pure ionic liquids within the framework of the quantum mechanics/molecular mechanics method. Each type of ion (cation or anion) is considered as an independent entity quantum mechanically described that follows a differentiated path in the liquid. The method permits, through an iterative procedure, the full coupling between the polarized charge distribution of the ions and the liquid structure around them. The procedure has been tested with 1-ethyl-3-methylimidazolium tetrafluoroborate. It was found that, similar to non-polar liquids and as a consequence of the low value of the reaction field, the cation and anion charge distributions are hardly polarized by the rest of molecules in the liquid. Their structure is characterized by an alternance between anion and cation shells as evidenced by the coincidence of the first maximum of the anion-anion and cation-cation radial distribution functions with the first minimum of the anion-cation. Some degree of stacking between the cations is also found. PMID:26213207

  17. Importance of liquid fragility for energy applications of ionic liquids

    NASA Astrophysics Data System (ADS)

    Sippel, Pit; Lunkenheimer, Peter; Krohns, Stephan; Thoms, Erik; Loidl, Alois

    Ionic liquids (ILs) are salts that are liquid at ambient temperatures. The strong electrostatic forces between their molecular ions result, e.g., in low volatility and high stability for many members of this huge material class. For this reason they bear a high potential for new advancements in applications, e.g., as electrolytes in energy-storage devices such as supercapacitors or batteries, where the ionic conductivity is an essential figure of merit. Most ILs show dynamic properties typical for glassy matter, which dominate many of their physical properties. An important method to study these dynamical glass-properties is dielectric spectroscopy that can access relaxation times of dynamic processes and the conductivity in a broad frequency and temperature range. In the present contribution, we present results on a large variety of ionic liquids showing that the conductivity of ILs depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility. This work was supported by the Deutsche Forschungsgemeinschaft via Research Unit FOR1394 and by the BMBF via ENREKON 03EK3015.

  18. Molecular mechanisms of ionic liquid cytotoxicity probed by an integrated experimental and computational approach

    DOE PAGESBeta

    Yoo, Brian; Jing, Benxin; Jones, Stuart E.; Lamberti, Gary A.; Zhu, Yingxi; Shah, Jindal K.; Maginn, Edward J.

    2016-02-02

    Ionic liquids (ILs) are salts that remain liquid down to low temperatures, and sometimes well below room temperature. ILs have been called “green solvents” because of their extraordinarily low vapor pressure and excellent solvation power, but ecotoxicology studies have shown that some ILs exhibit greater toxicity than traditional solvents. A fundamental understanding of the molecular mechanisms responsible for IL toxicity remains elusive. Here we show that one mode of IL toxicity on unicellular organisms is driven by swelling of the cell membrane. Cytotoxicity assays, confocal laser scanning microscopy, and molecular simulations reveal that IL cations nucleate morphological defects in themore » microbial cell membrane at concentrations near the half maximal effective concentration (EC50) of several microorganisms. Lastly, cytotoxicity increases with increasing alkyl chain length of the cation due to the ability of the longer alkyl chain to more easily embed in, and ultimately disrupt, the cell membrane.« less

  19. Molecular mechanisms of ionic liquid cytotoxicity probed by an integrated experimental and computational approach

    PubMed Central

    Yoo, Brian; Jing, Benxin; Jones, Stuart E.; Lamberti, Gary A.; Zhu, Yingxi; Shah, Jindal K.; Maginn, Edward J.

    2016-01-01

    Ionic liquids (ILs) are salts that remain liquid down to low temperatures, and sometimes well below room temperature. ILs have been called “green solvents” because of their extraordinarily low vapor pressure and excellent solvation power, but ecotoxicology studies have shown that some ILs exhibit greater toxicity than traditional solvents. A fundamental understanding of the molecular mechanisms responsible for IL toxicity remains elusive. Here we show that one mode of IL toxicity on unicellular organisms is driven by swelling of the cell membrane. Cytotoxicity assays, confocal laser scanning microscopy, and molecular simulations reveal that IL cations nucleate morphological defects in the microbial cell membrane at concentrations near the half maximal effective concentration (EC50) of several microorganisms. Cytotoxicity increases with increasing alkyl chain length of the cation due to the ability of the longer alkyl chain to more easily embed in, and ultimately disrupt, the cell membrane. PMID:26831599

  20. Molecular mechanisms of ionic liquid cytotoxicity probed by an integrated experimental and computational approach.

    PubMed

    Yoo, Brian; Jing, Benxin; Jones, Stuart E; Lamberti, Gary A; Zhu, Yingxi; Shah, Jindal K; Maginn, Edward J

    2016-01-01

    Ionic liquids (ILs) are salts that remain liquid down to low temperatures, and sometimes well below room temperature. ILs have been called "green solvents" because of their extraordinarily low vapor pressure and excellent solvation power, but ecotoxicology studies have shown that some ILs exhibit greater toxicity than traditional solvents. A fundamental understanding of the molecular mechanisms responsible for IL toxicity remains elusive. Here we show that one mode of IL toxicity on unicellular organisms is driven by swelling of the cell membrane. Cytotoxicity assays, confocal laser scanning microscopy, and molecular simulations reveal that IL cations nucleate morphological defects in the microbial cell membrane at concentrations near the half maximal effective concentration (EC50) of several microorganisms. Cytotoxicity increases with increasing alkyl chain length of the cation due to the ability of the longer alkyl chain to more easily embed in, and ultimately disrupt, the cell membrane. PMID:26831599

  1. Layering of [BMIM]+-based ionic liquids at a charged sapphire interface

    NASA Astrophysics Data System (ADS)

    Mezger, Markus; Schramm, Sebastian; Schröder, Heiko; Reichert, Harald; Deutsch, Moshe; De Souza, Emerson J.; Okasinski, John S.; Ocko, Benjamin M.; Honkimäki, Veijo; Dosch, Helmut

    2009-09-01

    The structure of two model room temperature ionic liquids, [BMIM]+[PF6]- and [BMIM]+[BF4]-, near the solid/liquid interface with charged Al2O3(0001) (sapphire) was determined with subnanometer resolution by high energy (72.5 keV) x-ray reflectivity. [BMIM]+[PF6]- exhibits alternately charged, exponentially decaying, near-surface layering. By contrast, the smaller-anion compound, [BMIM]+[BF4]-, shows only a single layer of enhanced electron density at the interface. The different layering behaviors, and their characteristic length scales, correspond well to the different bulk diffraction patterns, also measured in this study. Complementary measurements of the surface and interface energies showed no significant different between the two RTILs. The combined bulk-interface results support the conclusion that the interfacial ordering is dominated by the same electrostatic ion-ion interactions dominating the bulk correlations, with hydrogen bonding and dispersion interactions playing only a minor role.

  2. Evaporation from an ionic liquid emulsion.

    PubMed

    Friberg, Stig E

    2007-03-15

    The conditions during evaporation in a liquid crystal-in-ionic liquid microemulsion (LC/microEm) were estimated using the phase diagram of the system. The equations for selected tie lines were established and the coordinates calculated for the sites, at which the evaporation lines crossed the tie lines. These values combined with the coordinates for the phases connecting the tie lines were used to calculate the amounts and the composition of the fractions of the two phases present in the emulsion during the evaporation. One of the emulsion phases was a lamellar liquid crystal and high energy emulsification would lead to the liquid crystal being disrupted to form vesicles. Such a system tenders a unique opportunity to study the interaction between vesicles and normal micelles, which gradually change to inverse micelles over bi-continuous structures. The amount of vesicles in the liquid phase versus the fraction liquid crystal was calculated for two extreme cases of vesicle core size and shell thickness. The limit of evaporation while retaining the vesicle structure was calculated for emulsions of different original compositions assuming the minimum continuous liquid phase to be 50% of the emulsion. PMID:17207810

  3. A morpholinium ionic liquid for cellulose dissolution.

    PubMed

    Raut, Dilip G; Sundman, Ola; Su, Weiqing; Virtanen, Pasi; Sugano, Yasuhito; Kordas, Krisztian; Mikkola, Jyri-Pekka

    2015-10-01

    A series of substituted morpholinium ionic salts and allyl ammonium acetates were prepared. Amongst those, N-allyl-N-methylmorpholinium acetate ([AMMorp][OAc]) was found to dissolve cellulose readily without any pre-processing of native cellulose. At 120°C, [AMMorp][OAc] could dissolve 30 wt%, 28 wt% and 25 wt% of cellulose with degree of polymerization (DPn) - 789, 1644 and 2082 respectively, in 20 min. Importantly, SEC analysis indicated that no discernible changes occurred in terms of the degree of polymerization of the different celluloses after regeneration. Furthermore, when comparing the cellulose dissolution capability of these newly synthesized ionic liquids, it is evident that the combination of all three constituents - the morpholinium cation, the existence of an allyl group and choosing the acetate anion are essential for efficient cellulose dissolution. The structure and morphology of the regenerated cellulosic materials were characterized by SEM, XRD, TGA, CP/MAS (13)C NMR and FTIR, respectively. PMID:26076596

  4. Metal ion adsorption at the ionic liquid-mica interface

    NASA Astrophysics Data System (ADS)

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G.; Atkin, Rob

    2015-12-01

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ~60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al3+ system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made.Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete

  5. Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid

    NASA Astrophysics Data System (ADS)

    Berger, Claudia A.; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

    2016-07-01

    The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important

  6. Characteristics of an ionic liquid electrolyte for sodium-ion batteries

    NASA Astrophysics Data System (ADS)

    Hasa, Ivana; Passerini, Stefano; Hassoun, Jusef

    2016-01-01

    We study the liquid mixture of sodium bis(trifluoromethanesulfonyl)imide in N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI-NaTFSI) for application in sodium-ion batteries. The ionic liquid-based electrolyte is characterized in terms of electrochemical and thermal properties. Ionic conductivity and electrochemical stability windows are evaluated through electrochemical impedance spectroscopy (EIS) measurements and voltammetry tests, respectively. The thermal stability is evaluated by differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). Moreover, the suitability of the IL-electrolyte is preliminary verified in half and in full-cells at room temperature, using P2-Na0.6Ni0.22Fe0.11Mn0.66O2 layered oxide cathode and nanostructured Sb-C composite anode. The cell shows promising characteristics with a working voltage of about 2.7 V and a delivered capacity of about 100 mAh g-1. Despite requiring further optimization in terms of cycle life and energy density, the data here reported suggest the suitability of the ionic liquid electrolyte for application in sodium-ion battery.

  7. Interactions in the ionic liquid [EMIM][FAP]: a coupled experimental and computational analysis.

    PubMed

    Voroshylova, Iuliia V; Teixeira, Filipe; Costa, Renata; Pereira, Carlos M; Cordeiro, M Natália D S

    2016-01-28

    Gas-phase electronic and structural properties of the room temperature ionic liquid 1-ethyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate ([EMIM][FAP]) were studied using density functional theory, and confirmed with results from infrared spectroscopy. A conformational analysis allowed the identification of several plausible conformers of the ion pairs. For the detected conformers, the infrared spectra were predicted and their thermodynamic properties were evaluated. The topology of the electronic density of the most stable conformers of [EMIM][FAP] ion pairs were characterised using the quantum theory of atoms in molecules. A number of possible hydrogen bonds between the cations and anions of the ionic liquid were identified. Excellent correspondence was found between the predicted spectra of gas-phase [EMIM][FAP] conformers and the experimental infrared spectrum, which in turn allowed a clear attribution of the vibration modes of [EMIM][FAP]. Finally, the contribution of the various conformers of both isomers of the [FAP](-) anion to the ionic liquid macro-properties is shown. PMID:26699428

  8. Diffusion and structure in complex fluids: I. Axial diffusion in membranes II. Proteins in ionic liquids

    NASA Astrophysics Data System (ADS)

    Bihari, Malvika

    Geometrically hindered motions of a single large solute (particle or polymer) can be imaged in real time via optical microscopy. The dynamics of fluorescent colloidal particles near surfaces and in porous membranes were monitored using confocal microscopy. A method of analysis to estimate diffusivity of particles in the axial direction by observing their intensity fluctuations was developed. The intensity fluctuations correspond to the Brownian motion of the particles in the axial direction. The method was successful in capturing the hindered diffusion of particles close to surfaces and in pores. This study provides a novel route to monitor the dynamics of particles, including biomacromolecules, near surfaces, through porous substrates and biological tissues. Ionic liquid (IL) as a medium for room temperature preservation of biomacromolecules has been proposed and, to investigate the possibility, physicochemical and enzymatic properties of proteins in the neat hydrophilic IL, ethylmethyl imidazolium ethyl sulfate [EMIM][EtSO4] were studied. Spectroscopic techniques were employed to probe the secondary and tertiary structure of proteins whereas light scattering and viscometry were used to estimate the hydrodynamic size. The secondary structure of the protein was retained in the ionic liquid but the tertiary structure was found to change. Alterations in protein conformation/activity were investigated after transfer of the dissolved protein from the IL to buffer. Further, suitability of ionic liquid gels as protein encapsulation and preservation media was assessed.

  9. Electrotunable Lubricity with Ionic Liquid Nanoscale Films

    PubMed Central

    Fajardo, O. Y.; Bresme, F.; Kornyshev, A. A.; Urbakh, M.

    2015-01-01

    One of the main challenges in tribology is finding the way for an in situ control of friction without changing the lubricant. One of the ways for such control is via the application of electric fields. In this respect a promising new class of lubricants is ionic liquids, which are solvent-free electrolytes, and their properties should be most strongly affected by applied voltage. Based on a minimal physical model, our study elucidates the connection between the voltage effect on the structure of the ionic liquid layers and their lubricating properties. It reveals two mechanisms of variation of the friction force with the surface charge density, consistent with recent AFM measurements, namely via the (i) charge effect on normal and in-plane ordering in the film and (ii) swapping between anion and cation layers at the surfaces. We formulate conditions that would warrant low friction coefficients and prevent wear by resisting “squeezing-out” of the liquid under compression. These results give a background for controllable variation of friction. PMID:25572127

  10. On the radiation stability of crown ethers in ionic liquids.

    SciTech Connect

    Shkrob, I.; Marin, T.; Dietz, M.

    2011-04-14

    Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a 'radioprotective' effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

  11. Metal ion adsorption at the ionic liquid-mica interface.

    PubMed

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G; Atkin, Rob

    2016-01-14

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ∼60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al(3+) system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made. PMID:26661934

  12. Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid.

    PubMed

    Berger, Claudia A; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

    2016-08-01

    The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer. PMID:27121463

  13. Ionic Liquid Structure-Induced Effects on Organic Reactions

    NASA Astrophysics Data System (ADS)

    Stark, Annegret

    Understanding the ways in which the constituents of ionic liquids, i.e. the type of cation, its substitution, and the type of anion chosen, interact with reactants is prerequisite to deliberately designing an ionic liquid solvent with optimum performance. Several approaches, including physico-chemical and spectroscopic measurements and computational studies of binary ionic liquid-substrate mixtures have been presented that investigate the strength of interactions.

  14. Ionic Liquid assisted Synthesis of Zeolite-TON

    PubMed Central

    Tian, Yuyang; McPherson, Matthew J; Wheatley, Paul S; Morris, Russell E

    2014-01-01

    An ionic liquid assisted strategy for the synthesis of zeolitic material is reported. This strategy is a solid state synthetic method and the ionic liquid is employed as structure directing agent. A TON-type zeolite, which contains one-dimensional 10-member-ring, is successfully synthesized with the assistance of the ionic liquid, 1-ethyl-3-methylimidazolium bromide. This finding improves our understanding about the challenge of ionothermally synthesizing siliceous and aluminosilicate zeolites. PMID:26213423

  15. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

    2005-11-01

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

  16. Ionic Liquids and Ionizing Radiation: Reactivity of Highly Energetic Species

    SciTech Connect

    Wishart, J.F.

    2010-11-04

    Due to their unique properties, ionic liquids present many opportunities for basic research on the interactions of radiation with materials under conditions not previously available. At the same time, there are practical applied reasons for characterizing, understanding, and being able to predict how ionic-liquid-based devices and industrial-scale systems will perform under conditions of extreme reactivity, including radiation. This perspective discusses current issues in ionic liquid physical chemistry, provides a brief introduction to radiation chemistry, draws attention to some key findings in ionic liquid radiation chemistry, and identifies some current hot topics and new opportunities.

  17. Highly luminescent and color-tunable salicylate ionic liquids

    DOE PAGESBeta

    Campbell, Paul S.; Yang, Mei; Pitz, Demian; Cybinska, Joanna; Mudring, Anja -Verena

    2014-03-11

    High quantum yields of up to 40.5 % can be achieved in salicylate-bearing ionic liquids. A range of these ionic liquids have been synthesized and their photoluminescent properties studied in detail. The differences noted can be related back to the structure of the ionic liquid cation and possible interionic interactions. It is found that shifts of emission, particularly in the pyridinium-based ionic liquids, can be related to cation–anion pairing interactions. Furthermore, facile and controlled emission color mixing is demonstrated through combining different ILs, with emission colors ranging from blue to yellow.

  18. Highly luminescent and color-tunable salicylate ionic liquids.

    PubMed

    Campbell, Paul S; Yang, Mei; Pitz, Demian; Cybinska, Joanna; Mudring, Anja-Verena

    2014-04-14

    High quantum yields of up to 40.5% can be achieved in salicylate-bearing ionic liquids. A range of these ionic liquids have been synthesized and their photoluminescent properties studied in detail. The differences noted can be related back to the structure of the ionic liquid cation and possible interionic interactions. It is found that shifts of emission, particularly in the pyridinium-based ionic liquids, can be related to cation-anion pairing interactions. Facile and controlled emission color mixing is demonstrated through combining different ILs, with emission colors ranging from blue to yellow. PMID:24615781

  19. Lipid extraction from microalgae using a single ionic liquid

    DOEpatents

    Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

    2013-05-28

    A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

  20. Determination of solubility parameters of ionic liquids and ionic liquid/solvent mixtures from intrinsic viscosity.

    PubMed

    Weerachanchai, Piyarat; Wong, Yuewen; Lim, Kok Hwa; Tan, Timothy Thatt Yang; Lee, Jong-Min

    2014-11-10

    The total and partial solubility parameters (dispersion, polar and hydrogen-bonding solubility parameters) of ten ionic liquids were determined. Intrinsic viscosity approaches were used that encompassed a one-dimensional method (1D-Method), and two different three-dimensional methods (3D-Method1 and 3D-Method2). The effect of solvent type, the dimethylacetamide (DMA) fraction in the ionic liquid, and dissolution temperature on solubility parameters were also investigated. For all types of effect, both the 1D-Method and 3D-Method2 present the same trend in the total solubility parameter. The partial solubility parameters are influenced by the cation and anion of the ionic liquid. Considering the effect on partial solubility parameters of the solvent type in the ionic liquid, it was observed that in both 3D methods, the dispersion and polar parameters of a 1-ethyl-3-methylimidazolium acetate/solvent (60:40 vol %) mixture tend to increase as the total solubility parameter of the solvent increases. PMID:25145759

  1. Aprotic Heterocyclic Anion Triazolide Ionic Liquids - A New Class of Ionic Liquid Anion Accessed by the Huisgen Cycloaddition Reaction

    SciTech Connect

    Thompson, Robert L; Damodaran, Krishnan; Luebke, David; Nulwala, Hunaid

    2013-06-01

    The triazole core is a highly versatile heterocyclic ring which can be accessed easily with the Cu(I)-catalyzed Huisgen cycloaddition reaction. Herein we present the preparation of ionic liquids that incorporate a 1,2,3-triazolide anion. These ionic liquids were prepared by a facile procedure utilizing a base-labile pivaloylmethyl group at the 1-position, which can act as precursors to 1H- 4-substituted 1,2,3-triazole. These triazoles were then subsequently converted into ionic liquids after deprotonation using an appropriate ionic liquid cation hydroxide. The densities and thermal decompositions of these ionic liquids were measured. These novel ionic liquids have potential applications in gas separations and in metal-free catalysis.

  2. Extraction of proteins with ionic liquid aqueous two-phase system based on guanidine ionic liquid.

    PubMed

    Zeng, Qun; Wang, Yuzhi; Li, Na; Huang, Xiu; Ding, Xueqin; Lin, Xiao; Huang, Songyun; Liu, Xiaojie

    2013-11-15

    Eight kinds of green ionic liquids were synthesized, and an ionic liquid aqueous two-phase system (ILATPS) based on 1,1,3,3-tetramethylguandine acrylate (TMGA) guanidine ionic liquid was first time studied for the extraction of proteins. Single factor experiments proved that the extraction efficiency of bovine serum albumin (BSA) was influenced by the mass of IL, K2HPO4 and BSA, also related to the separation time and temperature. The optimum conditions were determined through orthogonal experiment by the five factors described above. The results showed that under the optimum conditions, the extraction efficiency could reach up to 99.6243%. The relative standard deviations (RSD) of extraction efficiencies in precision experiment, repeatability experiment and stability experiment were 0.8156% (n=5), 1.6173% (n=5) and 1.6292% (n=5), respectively. UV-vis and FT-IR spectra confirmed that there were no chemical interactions between BSA and ionic liquid in the extraction process, and the conformation of the protein was not changed after extraction. The conductivity, DLS and TEM were combined to investigate the microstructure of the top phase and the possible mechanism for the extraction. The results showed that hydrophobic interaction, hydrogen bonding interaction and the salt out effect played important roles in the transferring process, and the aggregation and embrace phenomenon was the main driving force for the separation. All these results proved that guanidine ionic liquid-based ATPSs have the potential to offer new possibility in the extraction of proteins. PMID:24148423

  3. Predictive thermodynamics for ionic solids and liquids.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

    The application of thermodynamics is simple, even if the theory may appear intimidating. We describe tools, developed over recent years, which make it easy to estimate often elusive thermodynamic parameter values, generally (but not exclusively) for ionic materials, both solid and liquid, as well as for their solid hydrates and solvates. The tools are termed volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR), supplemented by the simple salt approximation (SSA) and single-ion values for volume, Vm, heat capacity, , entropy, , formation enthalpy, ΔfH°, and Gibbs formation energy, ΔfG°. These tools can be applied to provide values of thermodynamic and thermomechanical properties such as standard enthalpy of formation, ΔfH°, standard entropy, , heat capacity, Cp, Gibbs function of formation, ΔfG°, lattice potential energy, UPOT, isothermal expansion coefficient, α, and isothermal compressibility, β, and used to suggest the thermodynamic feasibility of reactions among condensed ionic phases. Because many of these methods yield results largely independent of crystal structure, they have been successfully extended to the important and developing class of ionic liquids as well as to new and hypothesised materials. Finally, these predictive methods are illustrated by application to K2SnCl6, for which known experimental results are available for comparison. A selection of applications of VBT and TDR is presented which have enabled input, usually in the form of thermodynamics, to be brought to bear on a range of topical problems. Perhaps the most significant advantage of VBT and TDR methods is their inherent simplicity in that they do not require a high level of computational expertise nor expensive high-performance computation tools - a spreadsheet will usually suffice - yet the techniques are extremely powerful and accessible to non-experts. The connection between formula unit volume, Vm, and standard thermodynamic parameters represents a

  4. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  5. Oxygen Extraction from Regolith Using Ionic Liquids

    NASA Technical Reports Server (NTRS)

    Barrios, Elizabeth A.; Curreri, Peter A.; Karr, Laurel J.

    2011-01-01

    An important concern with long-duration manned space travel is the need to furnish enough materials to the vehicle, as well as the crew, for the duration of the mission. By extracting oxygen from the oxides present in regolith, propellant and life support could be supplied to the vehicle and the crew while in space, thereby limiting the amount of supplies needed prior to lift-off. Using a class of compounds known as ionic liquids, we have been able to lower the electrolysis operating temperature from 1600 C (molten oxide electrolysis) to less than 200 C, making this process much more feasible in terms of energy consumption and materials handling. To make this process ready for deployment into space, we have investigated what steps of the process would be affected by the low-gravity environment in space. In the lab, the solubilization of lunar regolith simulant in ionic liquid produces water vapor that is normally distilled out of solution and subsequently electrolyzed for oxygen production. This distillation is not possible in space, so we have tested a method known as pervaporation and have suggested a way this technique could be incorporated into a reactor design.

  6. Design of ionic liquids for lipase purification.

    PubMed

    Ventura, Sónia P M; Sousa, Sílvia G; Freire, Mara G; Serafim, Luísa S; Lima, Alvaro S; Coutinho, João A P

    2011-09-15

    Aqueous two-phase systems (ATPS) are considered as efficient downstream processing techniques in the production and purification of enzymes, since they can be considered harmless to biomolecules due to their high water content and due to the possibility of maintaining a neutral pH value in the medium. A recent type of alternative ATPS is based on hydrophilic ionic liquids (ILs) and salting-out inducing salts. The aim of this work was to study the lipase (Candida antarctica lipase B - CaLB) partitioning in several ATPS composed of ionic liquids (ILs) and inorganic salts, and to identify the best IL for the enzyme purification. For that purpose a wide range of IL cations and anions, and some of their combinations were studied. For each system the enzyme partitioning between the two phases was measured and the purification factors and enzyme recoveries were determined. The results indicate that the lipase maximum purification and recovery were obtained for cations with a C(8) side alkyl chain, the [N(CN)(2)] anion and ILs belonging to the pyridinium family. However, the highest purification parameters were observed for 1-methyl-3-octylimidazolium chloride [C(8)mim]Cl, suggesting that the IL extraction capability does not result from a cumulative character of the individual characteristics of ILs. The results indicate that the IL based ATPS have an improved performance in the lipase purification and recovery. PMID:21852207

  7. Ionic liquid nanostructure enables alcohol self assembly.

    PubMed

    Murphy, Thomas; Hayes, Robert; Imberti, Silvia; Warr, Gregory G; Atkin, Rob

    2016-05-14

    Weakly structured solutions are formed from mixtures of one or more amphiphiles and a polar solvent (usually water), and often contain additional organic components. They contain solvophobic aggregates or association structures with incomplete segregation of components, which leads to a poorly defined interfacial region and significant contact between the solvent and aggregated hydrocarbon groups. The length scales, polydispersity, complexity and ill-defined structures in weakly structured solutions makes them difficult to probe experimentally, and obscures understanding of their formation and stability. In this work we probe the nanostructure of homogenous binary mixtures of the ionic liquid (IL) propylammonium nitrate (PAN) and octanol as a function of composition using neutron diffraction and atomistic empirical potential structure refinement (EPSR) fits. These experiments reveal why octanol forms weakly structured aggregates in PAN but not in water, the mechanism by which PAN stabilises the octanol assemblies, and how the aggregate morphologies evolve with octanol concentration. This new understanding provides insight into the general stabilisation mechanisms and structural features of weakly structured mixtures, and reveals new pathways for identifying molecular or ionic liquids that are likely to facilitate aggregation of non-traditional amphiphiles. PMID:27102801

  8. Physical properties and intermolecular dynamics of an ionic liquid compared with its isoelectronic neutral binary solution.

    PubMed

    Shirota, Hideaki; Castner, Edward W

    2005-10-27

    In this study, we address the following question about room-temperature ionic liquids (RTILs). Are the properties of a RTIL more dependent on the charges of the molecular ions or on the fact that the liquid is a complex mixture of two species, one or both of which are asymmetric? To address this question and to better understand the interactions and dynamics in RTILs, we have prepared the organic ionic liquid 1-methoxyethylpyridinium dicyanoamide (MOEPy(+)/DCA(-)) and compared this RTIL with the analogous isoelectronic binary solution, comprised of equal parts of 1-methoxyethylbenzene (MOEBz) and dicyanomethane (DCM). In essence, we have created a RTIL and a nearly identical neutral pair in which we have effectively turned off the charges. To understand the intermolecular interactions in both of these liquids, we have characterized the bulk density and shear viscosity. Using femtosecond optical Kerr effect spectroscopy, we have also characterized the intermolecular vibrational dynamics and diffusive reorientation. To verify that the shape, polarizability, and electronic structure of the RTIL ions and the components of the neutral pair are truly quite similar, we have carried out density functional theory calculations on the individual molecular ion and neutral species. PMID:16866386

  9. Self-assembling array of magnetoelectrostatic jets from the surface of a superparamagnetic ionic liquid.

    PubMed

    King, Lyon B; Meyer, Edmond; Hopkins, Mark A; Hawkett, Brian S; Jain, Nirmesh

    2014-12-01

    Electrospray is a versatile technology used, for example, to ionize biomolecules for mass spectrometry, create nanofibers and nanowires, and propel spacecraft in orbit. Traditionally, electrospray is achieved via microfabricated capillary needle electrodes that are used to create the fluid jets. Here we report on multiple parallel jetting instabilities realized through the application of simultaneous electric and magnetic fields to the surface of a superparamagnetic electrically conducting ionic liquid with no needle electrodes. The ionic liquid ferrofluid is synthesized by suspending magnetic nanoparticles in a room-temperature molten salt carrier liquid. Two ILFFs are reported: one based on ethylammonium nitrate (EAN) and the other based on EMIM-NTf2. The ILFFs display an electrical conductivity of 0.63 S/m and a relative magnetic permeability as high as 10. When coincident electric and magnetic fields are applied to these liquids, the result is a self-assembling array of emitters that are composed entirely of the colloidal fluid. An analysis of the magnetic surface stress induced on the ILFF shows that the electric field required for transition to spray can be reduced by as much as 4.5 × 10(7) V/m compared to purely electrostatic spray. Ferrofluid mode studies in nonuniform magnetic fields show that it is feasible to realize arrays with up to 16 emitters/mm(2). PMID:25372842

  10. Absorption and Oxidation of Nitrogen Oxide in Ionic Liquids.

    PubMed

    Kunov-Kruse, Andreas J; Thomassen, Peter L; Riisager, Anders; Mossin, Susanne; Fehrmann, Rasmus

    2016-08-01

    A new strategy for capturing nitrogen oxide, NO, from the gas phase is presented. Dilute NO gas is removed from the gas phase by ionic liquids under ambient conditions. The nitrate anion of the ionic liquid catalyzes the oxidation of NO to nitric acid by atmospheric oxygen in the presence of water. The nitric acid is absorbed in the ionic liquid up to approximately one mole HNO3 per mole of the ionic liquid due to the formation of hydrogen bonds. The nitric acid can be desorbed by heating, thereby regenerating the ionic liquid with excellent reproducibility. Here, time-resolved in-situ spectroscopic investigations of the reaction and products are presented. The procedure reveals a new vision for removing the pollutant NO by absorption into a non-volatile liquid and converting it into a useful bulk chemical, that is, HNO3 . PMID:27384885

  11. Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Goulbourne, N. C.

    2011-01-01

    Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an

  12. Reversible Carbene Formation in the Ionic Liquid 1-Ethyl-3-Methylimidazolium Acetate by Vaporization and Condensation.

    PubMed

    Kar, Bishnu Prasad; Sander, Wolfram

    2015-12-01

    The role of N-heterocyclic carbenes in the chemistry of ionic liquids based on imidazolium salts has long been discussed. Here, we present experimental evidence that 1-ethyl-3-methylimidazolium-2-ylidene (EMIm) can coexist with its protonated imidazolium cation (EMImH(+) ) at low temperatures. If the vapor of the ionic liquid [EMImH(+) ][AcO(-) ] is trapped in solid argon or nitrogen at 9 K, only acetic acid (AcOH) and the carbene, but no ionic species, are found by IR spectroscopy. This indicates that during the evaporation of [EMImH(+) ][AcO(-) ] proton transfer occurs to form the neutral species. If the vapor of [EMImH(+) ][AcO(-) ] is trapped at 9 K as film in the absence of a host matrix, a solid consisting of EMImH(+) , EMIm, AcO(-) , and AcOH is formed. During warming to room temperature the proton transfer in the solid to form back the IL [EMImH(+) ][AcO(-) ] can be monitored by IR spectroscopy. This clearly demonstrates that evaporation and condensation of the IL [EMImH(+) ][AcO(-) ] results in a double proton transfer, and the carbene EMIm is only metastable even at low temperatures. PMID:26376583

  13. Temperature-dependent structure of ionic liquids: X-ray scattering and simulations

    SciTech Connect

    Kashyap, Hemant K.; Santos, Cherry S.; Annapureddy, Harsha V.R.; Murthy, N. Sanjeeva; Margulis, Claudio J.; Castner, Jr., Edward W.

    2015-10-15

    In this article we determine the temperature-dependent structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid using a combination of X-ray scattering and molecular dynamics simulations. As in many other room-temperature ionic liquids three characteristic intermolecular peaks can be detected in the structure function S(q). A prepeak or first sharp diffraction peak is observed at about q = 0.42 {angstrom}{sup -1}. Long range anion-anion correlations are the most important contributors to this peak. In all systems we have studied to date, this prepeak is a signature of solvation asymmetry. The peak in S(q) near q = 0.75 {angstrom}{sup -1} is the signature of ionic alternation and arises from the charge ordered separation of ions of the same charge. The most intense diffraction peak near q = 1.37 {angstrom}{sup -1} arises from short-range separation between ions of opposite charge combined with a significant contribution from cationic carbon-carbon interactions, indicating that cationic hydrophobic tails have significant contacts.

  14. Tetraalkylphosphonium polyoxometalates : Electroactive, 'task-specific' ionic liquids.

    SciTech Connect

    Rickert, P. G.; Antonio, M. R.; Firestone, M. A.; Kubatko, K-A.; Szreder, T.; Wishart, J. F.; Dietz, M. L.; BNL; Univ. of Miami

    2007-01-01

    The pairing of selected polyoxometalate (POM) anions with appropriate tetraalkylphosphonium cations is shown to yield an original family of ionic liquids, among them an ambient-temperature 'liquid POM.'

  15. A step toward the development of high-temperature stable ionic liquid-in-oil microemulsions containing double-chain anionic surface active ionic liquid.

    PubMed

    Rao, Vishal Govind; Banerjee, Chiranjib; Ghosh, Surajit; Mandal, Sarthak; Kuchlyan, Jagannath; Sarkar, Nilmoni

    2013-06-20

    Owing to their fascinating properties and wide range of potential applications, interest in nonaqueous microemulsions has escalated in the past decade. In the recent past, nonaqueous microemulsions containing ionic liquids (ILs) have been utilized in performing chemical reactions, preparation of nanomaterials, synthesis of nanostructured polymers, and drug delivery systems. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions. Recently, surfactant-like properties of surface active ionic liquids (SAILs) have been used for preparation of microemulsions with high-temperature stability and temperature insensitivity. However, previously described methods present a limited possibility of developing IL-in-oil microemulsions with a wide range of thermal stability. With our previous work, we introduced a novel method of creating a huge number of IL-in-oil microemulsions (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B2012, 116, 2850-2855), composed of a SAIL as a surfactant, room-temperature ionic liquids as a polar phase, and benzene as a nonpolar phase. The use of benzene as a nonpolar solvent limits the application of the microemulsions to temperatures below 353 K. To overcome this limitation, we have synthesized N,N-dimethylethanolammonium 1,4-bis(2-ethylhexyl) sulfosuccinate (DAAOT), which was used as a surfactant. DAAOT in combination with isopropyl myristate (IPM, as an oil phase) and ILs (as a polar phase) produces a huge number of high-temperature stable IL-in-oil microemulsions. By far, this is the first report of a huge number of high-temperature stable IL-in-oil microemulsions. In particular, we demonstrate the wide range of thermal stability of [C6mim][TF2N]/DAAOT/IPM microemulsions by performing a phase behavior study, dynamic light scattering measurements, and (1)H NMR measurements and by using coumarin-480 (C-480) as a fluorescent probe

  16. Synthesis and characterization of ionic liquid immobilized on magnetic nanoparticles: A recyclable heterogeneous organocatalyst for the acetylation of alcohols

    NASA Astrophysics Data System (ADS)

    Ghorbani-Choghamarani, Arash; Norouzi, Masoomeh

    2016-03-01

    Herein, we describe a simple and efficient procedure for the preparation of 3-((3-(trisilyloxy)propyl)propionamide)-1-methylimidazolium chloride ionic liquid supported on magnetic nanoparticle (TPPA-IL-Fe3O4). The structure of this magnetic ionic liquid is fully characterized by FT-IR, TGA, XRD, VSM, SEM, EDX and DLS techniques. TPPA-IL-Fe3O4 is employed as a catalyst for the acetylation of alcohols with acetic anhydride under mild and heterogeneous conditions at room temperature with good to excellent yields. The magnetic catalyst could be readily separate from the reaction media by simple magnetic decantation, and reused several times without significant loss of its catalytic activity.

  17. Structural characterization and DFT study of V(IV)O(acac)2 in imidazolium ionic liquids.

    PubMed

    Mota, Andreia; Hallett, Jason P; Kuznetsov, Maxim L; Correia, Isabel

    2011-09-01

    We report the structural characterization of vanadyl acetylacetonate in imidazolium room temperature ionic liquids--bbimNTf(2), bmimNTf(2), C(3)OmimNTf(2), bm(2)imNTf(2), bmimPF(6), bmimOTf, bmimBF(4), bmimMeCO(2), bmimMeSO(4), bmimMe(2)PO(4) and bmimN(CN)(2)--and organic solvents. The complex was characterized by visible electronic (Vis) and EPR spectroscopies. VO(acac)(2) shows solvatochromism in the selected ionic liquids and behaves as in organic solvents, evidencing coordination of the ionic liquid anion in the solvents with higher coordinating ability. The Lewis basicity order obtained for the IL anions was: PF(6)(-) < NTf(2)(-) < OTf(-)≈ MeCO(2)(-) < MeSO(4)(-) < BF(4)(-)≈ N(CN)(2)(-) < Me(2)PO(4)(-). The solvent effect on the spectroscopic data was tentatively examined using linear solvation energy relationships based on the Kamlet-Taft solvent scale (α, β and π*), however no suitable correlation was found with all data. The EPR characterization showed the presence of two isomers in bmimOTf, bmimMeCO(2) and bmimMe(2)PO(4), suggesting coordination of the ionic liquid anions in both equatorial and axial positions. The full geometry optimization of cis-/trans-VO(acac)(2)(OTf)(-) and cis-/trans-VO(acac)(2)(OTf)(mmim) structures was done at the B3P86/6-31G* level of theory. The calculations confirm that the anion OTf(-) is able to coordinate to VO(acac)(2) with the trans isomer being more stable than the cis by 4.8 kcal mol(-1). PMID:21789301

  18. Microfluidic aqueous two-phase extraction of bisphenol A using ionic liquid for high-performance liquid chromatography analysis.

    PubMed

    Qi, Linlin; Wang, Yunhua; Li, Yajie; Zheng, Guoxia; Li, Changping; Su, Hongzhen

    2015-05-01

    An aqueous two-phase microfluidics (ATPM) method suitable for selective extraction of bisphenol A (BPA) in aqueous samples was developed, and a functional ionic liquid of N, N, N-trioctyl ammonium propionate (TOAP) was specially employed for the formation of a parallel flow system. Based on the analytical model, we optimized the chip design into branch-connection length pattern to achieve maximum extraction efficiency (φ max) and ensure phase separation. In combining the design flexibility and ideal reaction activity of extractant (TOAP), the developed ATPM enabled a selective and effective extraction of BPA (φ max of 95% within 2 s) from phenol derivatives. Meanwhile, the total operation time and ionic liquid consumption of the microfluidic extraction were only 2.5 min and 5 μl, respectively. The ATPM can be run at normal pH and room temperature and showed no interferences from components found in tap or beach water. To be noted, this specific extraction system was applied in real water samples; the recoveries of standard addition for all water samples spiked with BPA were from 96 to 110%. Finally, successful reuse of the chip was also realized. In all cases, the developed microfluidic chip was proven to be useful as an effective and low consumption approach in extracting BPA and should be expanded as a "green" preparative method for high-performance liquid chromatography (HPLC) analysis. PMID:25796523

  19. Brownian dynamics determine universality of charge transport in ionic liquids

    SciTech Connect

    Sangoro, Joshua R; Iacob, Ciprian; Mierzwa, Michal; Paluch, Marian; Kremer, Friedrich

    2012-01-01

    Broadband dielectric spectroscopy is employed to investigate charge transport in a variety of glass-forming ionic liquids over wide frequency, temperature and pressure ranges. Using a combination of Einstein, Einstein-Smoluchowski, and Langevin relations, the observed universal scaling of charge transport in ionic liquids is traced back to the dominant role of Brownian dynamics.

  20. Ionic Liquids and Green Chemistry: A Lab Experiment

    ERIC Educational Resources Information Center

    Stark, Annegret; Ott, Denise; Kralisch, Dana; Kreisel, Guenter; Ondruschka, Bernd

    2010-01-01

    Although ionic liquids have been investigated as solvents for many applications and are starting to be used in industrial processes, only a few lab experiments are available to introduce students to these materials. Ionic liquids have been discussed in the context of green chemistry, but few investigations have actually assessed the degree of…

  1. Polarity of the interface in ionic liquid in oil microemulsions.

    PubMed

    Andújar-Matalobos, María; García-Río, Luis; López-García, Susana; Rodríguez-Dafonte, Pedro

    2011-11-01

    Ionic liquid based microemulsions were characterized by absorption solvatochromic shifts, (1)H NMR and kinetic measurements in order to investigate the properties of the ionic liquid within the restricted geometry provided by microemulsions and the interactions of the ionic liquid with the interface. Experimental results show a significant difference between the interfaces of normal water and the new ionic liquid microemulsions. Absorption solvatochromic shift experiments and kinetic studies on the aminolysis of 4-nitrophenyl laurate by n-decylamine show that the polarity at the interface of the ionic liquid in oil microemulsions (IL/O) is higher than at the interface of water in oil microemulsions (W/O) despite the fact that the polarity of [bmim][BF(4)(-)] is lower than the polarity of water. (1)H NMR experiments showed that an increase in the ionic liquid content of the microemulsion led to an increase in the interaction between [bmim][BF(4)(-)] and TX-100. The reason for the higher polarity of the microemulsions with the ionic liquid can be explained in terms of the incorporation of higher levels of the ionic liquid at the interface of the microemulsions, as compared to water in the traditional systems. PMID:21820124

  2. Classical density functional theory & simulations on a coarse-grained model of aromatic ionic liquids.

    PubMed

    Turesson, Martin; Szparaga, Ryan; Ma, Ke; Woodward, Clifford E; Forsman, Jan

    2014-05-14

    A new classical density functional approach is developed to accurately treat a coarse-grained model of room temperature aromatic ionic liquids. Our major innovation is the introduction of charge-charge correlations, which are treated in a simple phenomenological way. We test this theory on a generic coarse-grained model for aromatic RTILs with oligomeric forms for both cations and anions, approximating 1-alkyl-3-methyl imidazoliums and BF₄⁻, respectively. We find that predictions by the new density functional theory for fluid structures at charged surfaces are very accurate, as compared with molecular dynamics simulations, across a range of surface charge densities and lengths of the alkyl chain. Predictions of interactions between charged surfaces are also presented. PMID:24718295

  3. Extraction of copper and zinc-humic acid with an ionic liquid

    NASA Astrophysics Data System (ADS)

    Huang, H.-L.; Tseng, Ru-Ling

    2009-04-01

    Extraction of copper and zinc in the contaminated soil with a room temperature ionic liquid (RTIL) has been studied by X-ray absorption near edge structural (XANES) and X-ray absorption fine structural (EXAFS) spectroscopies in the present work. By the least-square fitted XANES spectra, the major copper and zinc species in the contaminated soil are adsorbed copper- and adsorbed zinc-humic acid (HA). In a short contact, 80% of copper and zinc in the contaminated soil was extracted into the RTIL. The fitted EXAFS spectra show that Cu-HA and Zn-HA in the RTIL possessed the Cu-O and ZnO (1st shell) bond distances of 1.96 and 1.82 Å, respectively. The possible reaction path involved in extraction of copper and zinc in the contaminated soil into the RTIL has also been pointed out. Keywords: RTIL; XANES; EXAFS

  4. Pressure-induced amorphization of ionic liquid [HMIM][PF6

    NASA Astrophysics Data System (ADS)

    Ren, Yufen; Li, Haining; Zhu, Xiang; Chen, Liucheng; Su, Lei; Yang, Kun; Yang, Guoqiang; Wang, Hua

    2015-06-01

    Phase behavior of ionic liquid [HMIM][PF6] has been investigated under high pressure up to 5.6 GPa at room temperature. The results indicated that [HMIM][PF6] might experience a phase transition at about 3.4 GPa upon compression, which could be identified as solidification to superpressurized glass by ruby R1 line broadening measurement and synchrotron X-ray diffraction (XRD) patterns. For conformational equilibrium, the fraction of all-anti (AAAA) conformer increased upon compression, while the conformational change was independent of temperature. These facts indicated that there were large differences of the structure in response to the extreme conditions, especially in the structure of the cation.

  5. Corrosion of stainless steel battery components by bis(fluorosulfonyl)imide based ionic liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Evans, Tyler; Olson, Jarred; Bhat, Vinay; Lee, Se-Hee

    2014-12-01

    While the anodic behavior of aluminum foil current collectors in imide-based room temperature ionic liquids (RTILs) is relatively well understood, interactions between such RTILs and other passive battery components have not been studied extensively. This study presents the solvent and potential dependent oxidation of SS316 coin-cell components in the N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide (PYR13FSI) RTIL. While this phenomenon prohibits high-voltage cycling of Li(Ni1/3Mn1/3Co1/3)O2 cathodes in SS316 coin-type cells, Al-clad cell components or alternative cell configurations can be utilized to avoid SS316 oxidation-induced cell failure.

  6. Direct dissolution of wet and saliferous marine microalgae by polar ionic liquids without heating.

    PubMed

    Fujita, Kyoko; Kobayashi, Daigo; Nakamura, Nobuhumi; Ohno, Hiroyuki

    2013-03-01

    We successfully dissolved wet and saliferous microalgae (WSM) in polar ionic liquids (ILs) under mild conditions. The Kamlet-Taft parameters, especially β for the ILs, were good predictors of the ability to dissolve WSM. 1-Ethyl-3-methylimidazolium methylphosphate ([C2mim][MeO(H)PO(2)]) was the IL that best dissolved WSM without heating. WSM (containing 95 wt% water) was mixed with [C2mim][MeO(H)PO(2)]; the WSM had dissolved completely within 30 min at room temperature with gentle stirring. The IL maintained its chemical structure after removal of the microalgae component, suggesting recyclable use. The concentration of contaminant mineral salts in the [C2mim][MeO(H)PO(2)] did not increase with increasing recycle number. The recycled [C2mim][MeO(H)PO(2)] maintained its ability to dissolve WSM regardless of the number of recycling studied here. PMID:23410933

  7. Spatially resolved electrochemistry in ionic liquids: surface structure effects on triiodide reduction at platinum electrodes.

    PubMed

    Aaronson, Barak D B; Lai, Stanley C S; Unwin, Patrick R

    2014-02-25

    Understanding the relationship between electrochemical activity and electrode structure is vital for improving the efficiency of dye-sensitized solar cells. Here, the reduction of triiodide to iodide in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) room temperature ionic liquid (RTIL) is investigated on polycrystalline platinum using scanning electrochemical cell microscopy (SECCM) and correlated to the crystallographic orientation from electron backscatter diffraction (EBSD). Although the rate determining step in all grains was the first electron transfer, significant grain-dependent variations in activity were revealed, with grains with a dominant (110) crystallographic character exhibiting higher catalytic activity compared to those with a major (100) orientation. The SECCM technique is demonstrated to resolve heterogeneity in activity, highlighting that methods incorporating polycrystalline electrodes miss vital details for understanding and optimizing electrocatalysts. An additional advantage of the SECCM over single-crystal techniques is its ability to probe high index facets. PMID:24479903

  8. Ultrasound promoted synthesis of quinolines using basic ionic liquids in aqueous media as a green procedure.

    PubMed

    Kowsari, Elaheh; Mallakmohammadi, M

    2011-01-01

    The basic ionic liquid (BIL) based on imidazolum cation efficiently catalyzes the condensation reaction of isatin with ketones by ultrasonic irradiation in aqueous media for quinoline synthesis. When two different α-protons are available in a ketone, a mixture of two quinolines is obtained. In this method, one of the quinolines with high selectivity is produced. Another significant advantage of this method is omission of subsidiary reactions, such as aldol condensation. Compared with conventional methods, the main advantages of the present procedure are its being a green method, its milder conditions, necessary shorter reaction time, and its higher yields and selectivity without the need for a transition metal catalyst. The use of BILs and ultrasound promoted this protocol under room temperature. By changing the type of BILs, ultrasonic irradiation time, and ultrasonic frequency, synthesis of quinolines is manageable. PMID:20719553

  9. Accurate measurements of thermodynamic properties of solutes in ionic liquids using inverse gas chromatography.

    PubMed

    Mutelet, Fabrice; Jaubert, Jean-Noël

    2006-01-13

    Activity coefficients at infinite dilution of 29 organic compounds in two room temperature ionic liquids were determined using inverse gas chromatography. The measurements were carried out at different temperatures between 323.15 and 343.15K. To establish the influence of concurrent retention mechanisms on the accuracy of activity coefficients at infinite dilution for 1-butyl-3-methylimidazolium octyl sulfate and 1-ethyl-3-methylimidazolium tosylate, phase loading studies of the net retention volume per gram of packing as a function of the percent phase loading were used. It is shown that most of the solutes are retained largely by partition with a small contribution from adsorption on 1-butyl-3-methylimidazolium octyl sulfate and that the n-alkanes are retained predominantly by interfacial adsorption on 1-ethyl-3-methylimidazolium tosylate. PMID:16310203

  10. MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

    2013-03-21

    Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results. PMID:23480174

  11. Ionic Liquid-Organic Carbonate Electrolyte Blends To Stabilize Silicon Electrodes for Extending Lithium Ion Battery Operability to 100 °C.

    PubMed

    Ababtain, Khalid; Babu, Ganguli; Lin, Xinrong; Rodrigues, Marco-Tulio F; Gullapalli, Hemtej; Ajayan, Pulickel M; Grinstaff, Mark W; Arava, Leela Mohana Reddy

    2016-06-22

    Fabrication of lithium-ion batteries that operate from room temperature to elevated temperatures entails development and subsequent identification of electrolytes and electrodes. Room temperature ionic liquids (RTILs) can address the thermal stability issues, but their poor ionic conductivity at room temperature and compatibility with traditional graphite anodes limit their practical application. To address these challenges, we evaluated novel high energy density three-dimensional nano-silicon electrodes paired with 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide (Pip) ionic liquid/propylene carbonate (PC)/LiTFSI electrolytes. We observed that addition of PC had no detrimental effects on the thermal stability and flammability of the reported electrolytes, while largely improving the transport properties at lower temperatures. Detailed investigation of the electrochemical properties of silicon half-cells as a function of PC content, temperature, and current rates reveal that capacity increases with PC content and temperature and decreases with increased current rates. For example, addition of 20% PC led to a drastic improvement in capacity as observed for the Si electrodes at 25 °C, with stability over 100 charge/discharge cycles. At 100 °C, the capacity further increases by 3-4 times to 0.52 mA h cm(-2) (2230 mA h g(-1)) with minimal loss during cycling. PMID:27237138

  12. Electrodrift purification of materials for room temperature radiation detectors

    DOEpatents

    James, Ralph B.; Van Scyoc, III, John M.; Schlesinger, Tuviah E.

    1997-06-24

    A method of purifying nonmetallic, crystalline semiconducting materials useful for room temperature radiation detecting devices by applying an electric field across the material. The present invention discloses a simple technology for producing purified ionic semiconducting materials, in particular PbI.sub.2 and preferably HgI.sub.2, which produces high yields of purified product, requires minimal handling of the material thereby reducing the possibility of introducing or reintroducing impurities into the material, is easy to control, is highly selective for impurities, retains the stoichiometry of the material and employs neither high temperatures nor hazardous materials such as solvents or liquid metals. An electric field is applied to a bulk sample of the material causing impurities present in the sample to drift in a preferred direction. After all of the impurities have been transported to the ends of the sample the current flowing through the sample, a measure of the rate of transport of mobile impurities, falls to a low, steady state value, at which time the end sections of the sample where the impurities have concentrated are removed leaving a bulk sample of higher purity material. Because the method disclosed here only acts on the electrically active impurities, the stoichiometry of the host material remains substantially unaffected.

  13. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

    NASA Astrophysics Data System (ADS)

    Fadeeva, Tatiana A.; Husson, Pascale; DeVine, Jessalyn A.; Costa Gomes, Margarida F.; Greenbaum, Steven G.; Castner, Edward W.

    2015-08-01

    We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyze the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies.

  14. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

    SciTech Connect

    Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W.; Husson, Pascale; Costa Gomes, Margarida F.; Greenbaum, Steven G.

    2015-08-14

    We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyze the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies.

  15. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids.

    PubMed

    Fadeeva, Tatiana A; Husson, Pascale; DeVine, Jessalyn A; Costa Gomes, Margarida F; Greenbaum, Steven G; Castner, Edward W

    2015-08-14

    We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyze the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies. PMID:26277141

  16. Intermolecular vibrations and fast relaxations in supercooled ionic liquids

    NASA Astrophysics Data System (ADS)

    Ribeiro, Mauro C. C.

    2011-06-01

    Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < ω < 100 cm-1) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (˜19 Å) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids.

  17. Durable Electrooptic Devices Comprising Ionic Liquids

    DOEpatents

    Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

    2008-11-11

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

  18. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

    2009-12-15

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

  19. New triazolium based ionic liquid crystals

    SciTech Connect

    Stappert, Kathrin; Unal, Derya; Mallick, Bert; Mudring, Anja-Verena

    2014-01-01

    A set of novel 1,2,3-triazolium based ionic liquid crystals was synthesized and their mesomorphic behaviour studied by DSC (differential scanning calorimetry), POM (polarizing optical microscopy) and SAXS (small angle X-ray scattering). Beside the variation of the chain length (C10, C12 and C14) at the 1,2,3-triazolium cation also the anion has been varied (Br-, I-, I3-, BF4-, SbF6-, N(CN)2-, Tf2N-) to study the influence of ion size, symmetry and H-bonding capability on the mesophase formation. Interestingly, for the 1,3-didodecyl-1,2,3-triazolium cation two totally different conformations were found in the crystal structure of the bromide (U-shaped) and the triiodide (rod shaped).

  20. Microregion detection of ionic liquid microemulsions.

    PubMed

    Gao, Yanan; Wang, Suqing; Zheng, Liqiang; Han, Shuaibing; Zhang, Xuan; Lu, Deming; Yu, Li; Ji, Yongqiang; Zhang, Gaoyong

    2006-09-15

    Nonaqueous ionic liquid (IL) microemulsion consisting of IL, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), surfactant TX-100, and toluene was prepared and the phase behavior of the ternary system was investigated. Electrical conductivity measurement was used for investigating the microregions of the nonaqueous IL microemulsions. On the basis of the percolation theory, the bmimBF(4)-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF(4) (O/IL) microregions of the microemulsions were successfully identified using insulative toluene as the titration phase. However, this method was invalid when conductive bmimBF(4) acted as the titration phase. The microregions obtained by conductivity measurements were further proved by electrochemical cyclic voltammetry experiments. The results indicated that the conductivity method was feasible for identifying microstructures of the nonaqueous IL microemulsions. PMID:16765365