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Sample records for room-temperature ionic liquid

  1. 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 broadening by observing ~ 100 fs time scale oscillations in the shape of the 2D IR spectra.

  2. BIOELECTROCATALYTIC REACTIONS IN ROOM TEMPERATURE IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The direct electrochemical reduction of hemin, protopophyrin(IX) iron(III) chloride, ligated with strong or weak heterocyclic bases, was investigated in the ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][...

  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. ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

    PubMed Central

    Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

    2009-01-01

    Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

  5. Contracting cardiomyocytes in hydrophobic room-temperature ionic liquid

    SciTech Connect

    Hoshino, Takayuki; Department of Bio-Application and System Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei-shi, Tokyo 184-8588 ; Fujita, Kyoko; Higashi, Ayako; Sakiyama, Keiko; Ohno, Hiroyuki; Morishima, Keisuke; Department of Bio-Application and System Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei-shi, Tokyo 184-8588

    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 8,8,8,8}][Ala], phosphoric acid derivatives [P{sub 8,8,8,8}][MeO(H)PO{sub 2}], and [P{sub 8,8,8,8}][C{sub 7}CO{sub 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.

  6. Room temperature ionic liquids and their mixtures: potential pharmaceutical solvents.

    PubMed

    Mizuuchi, H; Jaitely, V; Murdan, S; Florence, A T

    2008-04-23

    Room temperature ionic liquids (RTILs) are organic salts which are liquids at ambient temperature. Composed of relatively large asymmetric organic cations and inorganic or organic anions, they have generated interest as 'green' solvents. Here we report on the solvency of alkyl imidazolium salts (PF(6)(-)Br(-)Cl(-)) for poorly water-soluble model drugs, albendazole and danazol, indicating their potential application as pharmaceutical solvents/cosolvents. The solubility of albendazole, for example, is increased by more than 10,000 times by 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF(6)(-)). Ionic liquids can be water-miscible or water-immiscible. The aqueous miscibility of a poorly water-miscible RTIL such as of [bmim]PF(6)(-) can be improved by the inclusion of a second more miscible RTIL (e.g. 1-hexyl-3-methylimidazolium bromide ([hmim]Br(-))). The extent of improvement in water miscibility was found to correlate with the hydrophilicity of the second RTIL. This ability to modulate RTILs' aqueous miscibility increases their usefulness as pharmaceutical solvents. PMID:18291630

  7. Lipase activation and stabilization in room-temperature ionic liquids.

    PubMed

    Kaar, Joel L

    2011-01-01

    Widespread interest in the use of room temperature ionic liquids (RTILs) as solvents in anhydrous biocatalytic reactions has largely been met with underwhelming results. Enzymes are frequently inactivated in RTILs as a result of the influence of solvent on the enzyme's microenvironment, be it through interacting with the enzyme or enzyme-bound water molecules. The purpose of this chapter is to present a rational approach to mediate RTIL-enzyme interactions, which is essential if we are to realize the advantages of RTILs over conventional solvents for biocatalysis in full. The underlying premise for this approach is the stabilization of enzyme structure via multipoint covalent immobilization within a polyurethane foam matrix. Additionally, the approach entails the use of salt hydrates to control the level of hydration of the immobilized enzyme, which is critical to the activation of enzymes in nonaqueous media. Although lipase is used as a model enzyme, this approach may be effective in activating and stabilizing virtually any enzyme in RTILs. PMID:20865386

  8. 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.

  9. Alkylsulfuric acid ionic liquids: a promising class of strongly acidic room-temperature ionic liquids.

    PubMed

    Dupont, David; Renders, Evelien; Binnemans, Koen

    2016-03-17

    Strongly acidic (pKa ≈ -3.5) room-temperature ionic liquids (ILs) with -OSO3H functionalized cations are introduced. The strong acidity, easy synthesis, and better physical properties of these R-OSO3H ILs make them excellent alternatives to the well-known sulfonic acid (R-SO3H) ILs, especially in the domain of metal processing. PMID:26947544

  10. Phase transition and conductive acceleration of phosphonium-cation-based room-temperature ionic liquid.

    PubMed

    Seki, Shiro; Umebayashi, Yasuhiro; Tsuzuki, Seiji; Hayamizu, Kikuko; Kobayashi, Yo; Ohno, Yasutaka; Kobayashi, Takeshi; Mita, Yuichi; Miyashiro, Hajime; Terada, Nobuyuki; Ishiguro, Shin-ichi

    2008-11-21

    An unusual ionic conduction phenomenon related to the phase transition of a novel phosphonium-cation-based room-temperature ionic liquid (RTIL) is reported; we found that in the phase change upon cooling, a clear increase in ionic conductivity was seen as the temperature was lowered, which differs from widely known conventional RTILs; clearly, our finding of abnormality of the correlation between temperature change and ionic conduction is the first observation in the electrolyte field. PMID:18997945

  11. Hydrophilic interaction liquid chromatography for separation and quantification of selected room-temperature ionic liquids.

    PubMed

    Le Rouzo, Guillaume; Lamouroux, Christine; Bresson, Carole; Guichard, Aline; Moisy, Philippe; Moutiers, Gilles

    2007-09-14

    Hydrophilic interaction liquid chromatography (HILIC) is an alternative technique to ion pairing-reversed-phase liquid chromatography (IP-RPLC) and classical RPLC for separation of alkylimidazolium room-temperature ionic liquids (RTILs). Particularly, HILIC offers better retention and selectivity for short-chains RTILs imidazolium compounds. HILIC mechanisms were investigated by studying the influence of organic modifier content and salt concentration in the mobile phase. HILIC method was validated by quantifying 1-butyl-3-methylimidazolium cation (BMIM) degradation under gamma radiation at 2.5MGy. Development of separative reproducible analytical methods, including for low concentration, applicable to RTILs are today mandatory to improve RTILs chemistry. PMID:17640658

  12. Direct visualization of solution morphology of cellulose in ionic liquids by conventional TEM at room temperature.

    PubMed

    Luo, Nan; Lv, Yuxia; Wang, Dexiu; Zhang, Jinming; Wu, Jin; He, Jiasong; Zhang, Jun

    2012-06-25

    Taking advantage of the negligible vapor pressure and dissolving features of ionic liquids (ILs), the solution morphology and dissolution process of cellulose in ILs have been visualized directly by conventional transmission electron microscopy (TEM) at room temperature for the first time. PMID:22592351

  13. 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.

  14. 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.

  15. 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.

  16. Reversible swelling of the cell wall of poplar biomass by ionic liquid at room temperature

    PubMed Central

    Lucas, Marcel; Wagner, Greg L.; Nishiyama, Yoshiharu; Hanson, Leif; Samayam, Indira P.; Schall, Constance A.; Langan, Paul; Rector, Kirk D.

    2012-01-01

    Time-resolved autofluorescence, Raman microspectroscopy, and scanning microprobe X-ray diffraction were combined in order to characterize lignocellulosic biomass from poplar trees and how it changes during treatment with the ionic liquid 1-n-ethyl-3-methylimidazolium acetate (EMIMAC) at room temperature. The EMIMAC penetrates the cell wall from the lumen, swelling the cell wall by about a factor of two towards the empty lumen. However, the middle lamella remains unchanged, preventing the cell wall from swelling outwards. During this swelling, most of the cellulose microfibrils are solubi-lized but chain migration is restricted and a small percentage of microfibrils persist. When the EMIMAC is expelled, the cellulose recrystallizes as microfibrils of cellulose I. There is little change in the relative chemical composition of the cell wall after treatment. The action of EMIMAC on the poplar cell wall at room temperature would therefore appear to be a reversible swelling and a reversible decrystallization of the cell wall. PMID:21247757

  17. 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.

  18. 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

  19. 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

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

    PubMed

    Murugappan, Krishnan; Silvester, Debbie S

    2016-01-20

    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

  1. Equilibrium and dynamic charge storage in nanopores with room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Wu, Peng

    Electrochemical capacitors store electrical energy physically in the electrical double layers at the electrode/electrolyte interfaces. In spite of their high power density and extraordinary cyclability, the widespread deployment of electrochemical capacitors is limited by their moderate energy density. The current surge in interest in electrochemical capacitors is driven by recent breakthroughs in developing novel electrode and electrolyte materials. In particular, electrodes featuring sub-nanometer pores and room-temperature ionic liquids are promising materials for next-generation electrochemical capacitors. To realize the full potential of these materials, a basic understanding of the charge storage mechanisms in them is essential. In this dissertation, using atomistic simulations, we investigated the charge storage in sub-nanometer pores using room-temperature ionic liquids as electrolytes. These simulations of the equilibrium charge storage in slit-shaped nanopores in contact with room-temperature ionic liquids showed that the capacitance of the nanopores 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 confirms prior experimental observations. The right branch of the curve indirectly agrees with experimental findings that so far have received little attention. We also found that the charge storage in sub-nanometer pores follows a distinct voltage dependent behavior. At low voltages, charge storage is achieved by swapping co-ions in the pore with counter-ions in the bulk electrolytes. As voltage increases, further charge storage is due mainly to the removal of co-ions from the pore, leading to a capacitance increase. The capacitance eventually reaches a maximum when all co-ions are expelled from the pore. At even higher electrode voltages, additional charge storage is realized by counter-ion insertion into the pore, accompanied by a reduction of capacitance. The molecular origins of these phenomena were elucidated by a new theoretical framework we developed specifically for the charge storage in nanopores using solvent-free electrolytes. These simulations of the charging dynamics of sub-nanometer pores in contact with room-temperature ionic liquids showed that the charging of ionophilic pores, of width comparable to the size of ion, is a diffusive process. Such a process is often accompanied by overfilling and followed by de-filling. In sharp contrast to conventional expectations, charging is fast because ion diffusion during charging can be an order of magnitude faster than in the bulk, and charging itself is accelerated by the onset of collective modes. Further acceleration can be achieved using ionophobic pores by eliminating overfilling/de-filling and thus leading to charging behavior qualitatively different from that in conventional, ionophilic pores. Overall, our studies indicated that electrodes with sub-nanometer pores and room-temperature ionic liquids can potentially enable the development of electrochemical capacitors with concurrently high power and energy densities. The fundamental insights gained in our studies help guide the rational design and optimization of these materials to realize their full potentials.

  2. Orientational dynamics of room temperature ionic liquid/water mixtures: water-induced structure.

    PubMed

    Sturlaugson, Adam L; Fruchey, Kendall S; Fayer, Michael D

    2012-02-16

    Optical heterodyne detected optical Kerr effect (OHD-OKE) measurements on a series of 1-alkyl-3-methylimidazolium tetrafluoroborate room-temperature ionic liquids (RTILs) as a function of chain length and water concentration are presented. The pure RTIL reorientational dynamics are identical in form to those of other molecular liquids studied previously by OHD-OKE (two power laws followed by a single exponential decay at long times), but are much slower at room temperature. In contrast, the addition of water to the longer alkyl chain RTILs causes the emergence of a long time biexponential orientational anisotropy decay. Such distinctly biexponential 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 slow component for the longer chain RTILs does not obey the Debye-Stokes-Einstein (DSE) equation across the range of solutions, and thus we attribute it to slow cation reorientational diffusion caused by a stiffening of cation alkyl tail-tail associations. The fast component of the decay is assigned to the motions (wobbling) of the tethered imidazolium head groups. The wobbling-in-a-cone analysis provides estimates of the range of angles sampled by the imidazolium head group prior to the long time scale complete orientational randomization. The heterogeneous dynamics and non-DSE behavior observed here should have a significant effect on reaction rates in RTIL/water cosolvent mixtures. PMID:22224942

  3. Terahertz and Infrared Spectroscopy of Room-Temperature Imidazolium-Based Ionic Liquids.

    PubMed

    Yamada, Toshiki; Tominari, Yukihiro; Tanaka, Shukichi; Mizuno, Maya

    2015-12-24

    The terahertz- and infrared-frequency vibrational modes of various room-temperature imidazolium-based ionic liquids with molecular anions were examined extensively. We found that the molar-concentration-normalized absorption coefficient spectra in the low-wavenumber range for imidazolium cations with different alkyl-chain lengths were nearly identical for the same anion. Regarding the overall view of a wide range of imidazolium-based ionic liquids, we found that the reduced mass of the combination of an imidazolium-ring cation and the anion and the force constant play significant roles in determining the central frequency of the broad absorption band. In addition to these findings, we also discuss the correlation between the (+)C-H stretching vibrational modes in the 3000-3300 cm(-1) range of the infrared spectra and the intermolecular vibrational band in the low-wavenumber range. Finally, we describe some interesting characteristics of the intermolecular vibrational band observed in a wide range of imidazolium-based ionic liquids. PMID:26625193

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

    SciTech Connect

    Griffin, Phillip; Agapov, Alexander L; Sokolov, Alexei P

    2012-01-01

    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.

  5. Existence of optical phonons in the room temperature ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate

    PubMed Central

    Burba, Christopher M.; Frech, Roger

    2011-01-01

    The technologically important properties of room temperature ionic liquids (RTILs) are fundamentally linked to the ion–ion interactions present among the constituent ions. These ion–ion interactions in one RTIL (1-ethyl-3-methylimidazolium trifluoromethanesulfonate, [C2mim]CF3SO3) are characterized with transmission FTIR spectroscopy and polarized attenuated total reflection (ATR) FTIR spectroscopy. A quasilattice model is determined to be the best framework for understanding the ionic interactions. A novel spectroscopic approach is proposed to characterize the degree of order that is present in the quasilattice by comparing the dipole moment derivative calculated from two independent spectroscopic measurements: (1) the TO–LO splitting of a vibrational mode using dipolar coupling theory and (2) the optical constants of the material derived from polarized ATR experiments. In principle, dipole moment derivatives calculated from dipolar coupling theory should be similar to those calculated from the optical constants if the quasilattice of the RTIL is highly structured. However, a significant disparity for the two calculations is noted for [C2mim]CF3SO3, indicating that the quasilattice of [C2mim]CF3SO3 is somewhat disorganized. The potential ability to spectroscopically characterize the structure of the quasilattice, which governs the long-range ion–ion interactions in a RTIL, is a major step forward in understanding the interrelationship between the molecular-level interactions among the constituent ions of an ionic liquid and the important physical properties of the RTIL. PMID:21476760

  6. Electrochemistry of Hg(II) salts in room-temperature ionic liquids.

    PubMed

    Manan, Ninie S A; Aldous, Leigh; Alias, Yatimah; Compton, Richard G; Lagunas, M Cristina; Hardacre, Christopher

    2011-03-24

    The electrochemistry of HgCl(2) and [Hg(NTf(2))(2)] ([NTf(2)](-)=bis-{(trifluoromethyl)sulfonyl}imide) has been studied in room temperature ionic liquids. It has been found that the cyclic voltammetry of Hg(II) is strongly dependent on a number of factors (e.g., concentration, anions present in the mixture, and nature of the working electrode) and differs from that found in other media. Depending on conditions, the cyclic voltammetry of Hg(II) can give rise to one, two, or four reduction peaks, whereas the reverse oxidative scans show two to four peaks. Diffuse reflectance UV-vis spectroscopy and X-ray powder diffraction have been used to aid the assignment of the voltammetric waves. PMID:21355596

  7. Preparation of Biopolymer Fibers by Electrospinning from Room Temperature Ionic Liquids

    PubMed Central

    Viswanathan, Gunaranjan; Murugesan, Saravanababu; Pushparaj, Victor; Nalamasu, Omkaram; Ajayan, Pulickel M.; Linhardt, Robert J.

    2016-01-01

    Electrospinning is a versatile process used to prepare micro- and nano- sized fibers from various polymers dissolved in volatile solvents. In this report, cellulose and celluloseheparin composite fibers are prepared from nonvolatile room temperature ionic liquid (RTIL) solvents by electrospinning. RTILs are extracted from the biopolymer fiber after the fiber formation using a cosolvent. Micron to nanometer sized, branched fibers were obtained from 10% (w/w) concentration of polysaccharide biopolymer in RTIL solution with an applied voltage of 1520 kV. Celluloseheparin composite fibers showed anticoagulant activity, demonstrating that the bioactivity of heparin remained unaffected even on exposure to a high voltage involved in electrospinning. PMID:16471910

  8. 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.

  9. 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.

  10. The room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate: Electrochemical couples and physical properties

    SciTech Connect

    Fuller, J.; Carlin, R.T.; Osteryoung, R.A.

    1997-11-01

    Room temperature molten salts composed of the 1-ethyl-3-methylimidazolium cation and a chloroaluminate anion have received much attention for use in a variety of commercial applications such as batteries, photovoltaics, metal deposition, and capacitors. The room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF{sub 4}) was demonstrated as a versatile electrolyte by examining three representative electrochemical couples: ferrocene and tetrathiafulvalene oxidations and lithium ion reduction. Square-wave voltammetric data for ferrocene oxidation were fit to a reversible one-electron process using the COOL algorithm to give a half-wave potential of 0.490 V vs. Al/Al(III) and a diffusion coefficient of 5.1 {times} 10{sup {minus}7} cm{sup 2}/s. The two-electron oxidation of tetrathiafulvalene was reversible and proceeded through two consecutive one-electron steps; although data collected at lower square-wave frequencies indicated a slow precipitation of the TTF{sup +} species. Lithium ion was reduced to lithium metal at a Pt electrode following the addition of water to the EMIBF{sub 4} electrolyte, whereas lithium ion reduction at an Al wire produced the {beta}-LiAl alloy. Conductivities and kinematic viscosities of EMIBF{sub 4} were measured from 20 to 100 C and had values of 14 mS/cm and 0.275 cm{sup 2}/s, respectively, at 25 C.

  11. Determination of the physical properties of room temperature ionic liquids using a Love wave device.

    PubMed

    Ouali, F Fouzia; Doy, Nicola; McHale, Glen; Hardacre, Christopher; Ge, Rile; Allen, Ray W K; MacInnes, Jordan M; Newton, Michael I

    2011-09-01

    In this work, we have shown that a 100 MHz Love wave device can be used to determine whether room temperature ionic liquids (RTILs) are Newtonian fluids and have developed a technique that allows the determination of the density-viscosity product, ρη, of a Newtonian RTIL. In addition, a test for a Newtonian response was established by relating the phase change to insertion loss change. Five concentrations of a water-miscible RTIL and seven pure RTILs were measured. The changes in phase and insertion loss were found to vary linearly with the square root of the density-viscosity product for values up to (ρη)(1/2) ~ 10 kg m(-2) s(-1/2). The square root of the density-viscosity product was deduced from the changes in either phase or insertion loss using glycerol as a calibration liquid. In both cases, the deduced values of ρη agree well with those measured using viscosity and density meters. Miniaturization of the device, beyond that achievable with the lower-frequency quartz crystal microbalance approach, to measure smaller volumes is possible. The ability to fabricate Love wave and other surface acoustic wave sensors using planar metallization technologies gives potential for future integration into lab-on-a-chip analytical systems for characterizing ionic liquids. PMID:21786814

  12. 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.

  13. 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.

  14. 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 nanoparticles that resulted in the sample contraction and the deposition of nanoparticles onto the surface and embedded into the cell wall. To date, both silver and gold particles ranging in size from 40-100 nm have been incorporated into wood. Penetration of gold nanoparticles of 100 nm diameter in the cell walls was best confirmed by near-infrared confocal Raman microscopy, since the deposition of gold nanoparticles induces a significant enhancement of the Raman signal from the wood in their close proximity, an enhancement attributed to the surface-enhanced Raman effect (SERS). After rinsing with water, scanning electron microscopy (SEM) and Raman images of the same areas show that most nanoparticles remained on the pretreated sample. Raman images at different depths reveal that a significant number of nanoparticles were incorporated into the wood sample, at depths up to 4 {micro}m, or 40 times the diameter of the nanoparticles. Control experiments on an untreated wood sample resulted in the deposition of nanoparticles only at the surface and most nanoparticles were removed upon rinsing. This particle incorporation process enables the development of new pretreatments, since the nanoparticles have a high surface-to-volume ratio and could be chemically functionalized. Other potential applications for the incorporated nanoparticles include isotope tracing, catalysis, imaging agents, drug-delivery systems, energy-storage devices, and chemical sensors.

  15. 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

  16. Kinetics and Thermodynamics of Hydrogen Oxidation and Oxygen Reduction in Hydrophobic Room-Temperature Ionic Liquids

    PubMed Central

    Rollins, Julie B.; Conboy, John C.

    2010-01-01

    In this study 1-dodecyl-3-methylimidazolium (C12mim) bis(pentafluoroethylsulfonyl)imide (BETI) and 1-dodecylimidazolium (C12im) BETI hydrophobic room-temperature ionic liquids (RTILs) were synthesized and used as proton-conducting electrolytes in a nonhumidified feed gas electrochemical cell. The ionic conductivities of C12mimBETI and C12imBETI were similar and increased linearly with an increase in temperature from 20 to 130°C. However, when used in the electrochemical system the protic water-equilibrated C12imBETI had a larger maximum current and power density compared to the aprotic water-equilibrated C12mimBETI. The effect of water content on the reaction rates and thermodynamics of these hydrophobic RTILs was also examined. The efficiency of the C12mimBETI increased upon removal of water while that of the C12imBETI decreased in efficiency when water was removed. The water structure in these RTILs was examined using attenuated total internal reflection Fourier transform IR spectroscopy and depended on the chemical structure of the cation. These studies give further insight into the possible mechanism of proton transport in these RTIL systems. PMID:20414470

  17. 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...

  18. Evidence for laser-induced formation of solvated electrons in room temperature ionic liquids.

    PubMed

    Chandrasekhar, N; Endres, F; Unterreiner, A-N

    2006-07-21

    The photolytic generation of solvated electrons was observed for the first time in two room temperature ionic liquids (RTILs), trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide (IL) and 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide (IL). A 70 fs UV-pulse was used to excite the RTILs, while the transient response was monitored in the visible and near-infrared spectral regions. Immediately after excitation, a pulse duration limited rise of the induced absorption indicated the formation of solvated electrons suggesting the existence of pre-formed traps in RTILs. A broad transient absorption spectrum with a full width at half maximum of about 0.9 eV, typical for solvated electrons, was reconstructed from the transient profiles. Wavelength-independent relaxation dynamics at longer delay times suggest a lifetime of solvated electrons in the ns regime in agreement with results from pulse radiolysis studies. Adding 1,1-dimethylpyrrolidinium iodide to IL led to an increase of the UV absorbance and consequently, to an increase of the yield of solvated electrons. Furthermore, this solute is an efficient electron scavenger causing the transients to decay within about 40 ps. PMID:16902711

  19. 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).

  20. Room Temperature Ionic Liquid Electrolytes for Advanced Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Evans, Tyler

    This dissertation presents a series of studies aimed towards the development of a compelling and commercially viable Li-ion battery containing a non-flammable room temperature ionic liquid (RTIL) electrolyte. Each study builds upon the previous, culminating in the demonstration of a high energy Li-ion system approaching the 700 Wh/L energy density benchmark. We begin by tackling several major issues associated with RTIL compatibility with the battery's passive, non- electroactive components, engineering solutions to each and enabling the utilization of certain RTIL materials in high voltage Li-ion systems. Since enabling the simple use of our RTIL electrolytes, we have been able to explore RTIL compatibility with a number of attractive, next-generation electrode chemistries including the high capacity silicon (Si) anode and high voltage, high capacity lithium- manganese-rich (LMR) cathode. Each of these studies contributes to a deeper understanding of the interfacial mechanisms occurring between the RTIL materials and various electrode surfaces, in several cases resulting in unprecedented half- and full-cell performance. The accomplishments presented herein represent important progress in working towards a safer, higher performance Li-ion system.

  1. Coordination behavior and electrochemical studies of actinide and transition metal complexes in room temperature ionic liquids

    SciTech Connect

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

    2004-01-01

    Our current research efforts are centered around the behavior of actinide and transition metal complexes in room temperature ionic liquids (RTIL's). The RTIL's typically employed in our studies are based upon either cyclic or acyclic quaternary ammonium and 1,3-dialkylimidazolium cations with the bis(trifluoromethylsulfonyl)imide anion, [N(SO{sub 2}CF{sub 3}){sub 2}]{sup -}. Previous work in our group indicated that this anion has the ability to coordinate to metal centers, since which time we have undertaken studies to learn more about the fundamental coordination chemistry of this important anion. We have found that the [N(SO{sub 2}CF{sub 3}){sub 2}]{sup -} anion can coordinate to a metal center in both mono- and bidentate modes through oxygen and nitrogen atoms. These results will be demonstrated with single crystal structure representations of selected examples. Another aspect of our research includes electron transfer studies of metal complexes utilizing RTIL's as neat electrochemical solvents. Electrochemical experiments can provide insight into the reactivity and stability of charged species within RTIL's, an area of current fundamental importance. Results from voltammetric and bulk coulometric electron transfer studies on formal U(IV)/U(VI) complexes and transition metal systems will be presented.

  2. 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.

  3. 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

  4. Electrodeposition of metallic uranium at near ambient conditions from room temperature ionic liquid

    NASA Astrophysics Data System (ADS)

    Jagadeeswara Rao, Ch.; Venkatesan, K. A.; Nagarajan, K.; Srinivasan, T. G.; Vasudeva Rao, P. R.

    2011-01-01

    The electrochemical behavior of U(IV) in the room temperature ionic liquid (RTIL), N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPiNTf 2), was investigated to evaluate the feasibility of using the RTIL for non-aqueous reprocessing application. In this context, the rate of dissolution of uranium oxide (UO 2) in HNTf 2 was studied at 353 K. The dissolution of UO 2 in HNTf 2 was rapid; nearly 50% of UO 2 dissolved within 3 h and more than 95% dissolved in 25 h. The resultant solution was dried, diluted with MPPiNTf 2 and the electrochemical behavior of U(IV) in MPPiNTf 2 was studied at 373 K at platinum, glassy carbon and stainless steel electrodes. The cyclic voltammograms of U(IV) in MPPiNTf 2 at platinum and glassy carbon electrodes consisted of four cathodic waves occurring at a peak potentials of -0.7 V (Fc/Fc +), -1.4 V, -2.2 V and -2.7 V. Controlled potential electrolysis of a solution of U(IV) in MPPiNTf 2 at -2.8 V (Fc/Fc +) resulted in the deposition of metallic uranium, which was confirmed by X-ray diffraction and scanning electron microscopy.

  5. Stability of the Liquid State of Imidazolium-Based Ionic Liquids under High Pressure at Room Temperature.

    PubMed

    Yoshimura, Yukihiro; Shigemi, Machiko; Takaku, Mayumi; Yamamura, Misaho; Takekiyo, Takahiro; Abe, Hiroshi; Hamaya, Nozomu; Wakabayashi, Daisuke; Nishida, Keisuke; Funamori, Nobumasa; Sato, Tomoko; Kikegawa, Takumi

    2015-06-25

    To understand the stability of the liquid phase of ionic liquids under high pressure, we investigated the phase behavior of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ([Cnmim][BF4]) homologues with different alkyl chain lengths for 2 ≤ n ≤ 8 up to ∼7 GPa at room temperature. The ionic liquids exhibited complicated phase behavior, which was likely due to the conformational flexibility in the alkyl chain. The present results reveal that [Cnmim][BF4] falls into superpressed state around 2-3 GPa range upon compression with an implication of multiple phase or structural transitions to ∼7 GPa. Remarkably, a characteristic nanostructural organization in ionic liquids largely diminishes at the superpressed state. The behaviors of imidazolium-based ionic liquids can be classified into, at least, three patterns: (1) pressure-induced crystallization, (2) superpressurization upon compression, and (3) decompression-induced crystallization from the superpressurized glass. Interestingly, the high-pressure phase behavior was relevant to the glass transition behavior at low temperatures and ambient pressure. As n increases, the glass transition pressure (pg) decreases (from 2.8 GPa to ∼2 GPa), and the glass transition temperature increases. The results indicate that the p-T range of the liquid phase is regulated by the alkyl chain length of [Cnmim][BF4] homologues. PMID:25988295

  6. 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

  7. Understanding the impact of nanoscale aggregation on charge transport and structural dynamics in room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Griffin, Philip; Holt, Adam; Wang, Yangyang; Sokolov, Alexei

    2015-03-01

    Amphiphilic room temperature ionic liquids (ILs) segregate on the nanoscale, forming intricate networks of charge-rich ionic domains intercalated with charge-poor aliphatic domains. While this structural phenomenon has been well established through x-ray diffraction studies and atomistic MD simulations, the precise effects of nanophase segregation on ion transport and structural dynamics in ILs remains poorly understood. Using a combination of broadband dielectric spectroscopy, light scattering spectroscopy, and rheology, we have characterized the ionic conductivity, structural dynamics, and shear viscosity of a homologous series of quaternary ammonium ionic liquids over a wide temperature range. Upon increasing the length and volume fraction of the alkyl side chains of these quaternary ammonium ILs, ionic conductivity decreases precipitously, although no corresponding slowing of the structural dynamics is observed. Instead, we identify the dynamical signature of supramolecular aggregates. Our results directly demonstrate the role that chemical structure and ionic aggregation plays in determining the charge transport properties of amphiphilic ILs.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    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][PF6]) salts of the 1-buthyl-3-methylimidazolium ([bmim]+) 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]+ 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]+ and of POPC. The [bmim]+ 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 (DPOPC) does not reveal a clearly identifiable trend, since DPOPC increases upon addition of [bmim][Cl] and decreases in the [bmim][PF6] 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.

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

    PubMed

    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][PF6]) salts of the 1-buthyl-3-methylimidazolium ([bmim](+)) 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](+) 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](+) and of POPC. The [bmim](+) 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 (DPOPC) does not reveal a clearly identifiable trend, since DPOPC increases upon addition of [bmim][Cl] and decreases in the [bmim][PF6] 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. PMID:25833602

  11. 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

  12. 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.

  13. Room-Temperature Ionic Liquids: Excluded Volume and Ion Polarizability Effects in the Electrical Double-Layer Structure and Capacitance

    NASA Astrophysics Data System (ADS)

    Lauw, Y.; Horne, M. D.; Rodopoulos, T.; Leermakers, F. A. M.

    2009-09-01

    We study structures of room-temperature ionic liquids at electrified interfaces and the corresponding electrical double-layer capacities using a self-consistent mean-field theory. Ionic liquids are modeled as segmented dendrimers and the effective dielectric constant is calculated from the local distribution of ions to accommodate the excluded volume and the local dielectric screening effects. The resulting camel-shaped capacitance curve is further analyzed in terms of the thickness of alternating layers and the polarization of ions at electrified interfaces.

  14. 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.

  15. Room-temperature ionic liquids and composite materials: platform technologies for CO(2) capture.

    PubMed

    Bara, Jason E; Camper, Dean E; Gin, Douglas L; Noble, Richard D

    2010-01-19

    Clean energy production has become one of the most prominent global issues of the early 21st century, prompting social, economic, and scientific debates regarding energy usage, energy sources, and sustainable energy strategies. The reduction of greenhouse gas emissions, specifically carbon dioxide (CO(2)), figures prominently in the discussions on the future of global energy policy. Billions of tons of annual CO(2) emissions are the direct result of fossil fuel combustion to generate electricity. Producing clean energy from abundant sources such as coal will require a massive infrastructure and highly efficient capture technologies to curb CO(2) emissions. Current technologies for CO(2) removal from other gases, such as those used in natural gas sweetening, are also capable of capturing CO(2) from power plant emissions. Aqueous amine processes are found in the vast majority of natural gas sweetening operations in the United States. However, conventional aqueous amine processes are highly energy intensive; their implementation for postcombustion CO(2) capture from power plant emissions would drastically cut plant output and efficiency. Membranes, another technology used in natural gas sweetening, have been proposed as an alternative mechanism for CO(2) capture from flue gas. Although membranes offer a potentially less energy-intensive approach, their development and industrial implementation lags far behind that of amine processes. Thus, to minimize the impact of postcombustion CO(2) capture on the economics of energy production, advances are needed in both of these areas. In this Account, we review our recent research devoted to absorptive processes and membranes. Specifically, we have explored the use of room-temperature ionic liquids (RTILs) in absorptive and membrane technologies for CO(2) capture. RTILs present a highly versatile and tunable platform for the development of new processes and materials aimed at the capture of CO(2) from power plant flue gas and in natural gas sweetening. The desirable properties of RTIL solvents, such as negligible vapor pressures, thermal stability, and a large liquid range, make them interesting candidates as new materials in well-known CO(2) capture processes. Here, we focus on the use of RTILs (1) as absorbents, including in combination with amines, and (2) in the design of polymer membranes. RTIL amine solvents have many potential advantages over aqueous amines, and the versatile chemistry of imidazolium-based RTILs also allows for the generation of new types of CO(2)-selective polymer membranes. RTIL and RTIL-based composites can compete with, or improve upon, current technologies. Moreover, owing to our experience in this area, we are developing new imidazolium-based polymer architectures and thermotropic and lyotropic liquid crystals as highly tailorable materials based on and capable of interacting with RTILs. PMID:19795831

  16. 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 %.

  17. 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, 42 ps for methanol, and 88 ps for ethanol. The shape and volume of the probe, therefore, impact reorientation far more severely than they do spectral diffusion at long times, though these two processes occur on similar timescales at earlier times. PMID:26049428

  18. 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 fields.

  19. 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.

  20. 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

  1. 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.

  2. 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 complexes have been studied with various electrochemical methods including cyclic and square-wave voltammetry, chronoamperometry, and bulk coulometry. Results from these studies will be presented to show the general electron transfer behavior of metal complexes in the RTIL's. As an example, Figure 2 shows the difference in chemical stability of an electrogenerated U(V) anion for two uranyl (U(VI)O{sub 2}{sup 2+}) complexes due to the difference in ancillary ligands about the uranyl moiety. Figure 2a shows a cyclic voltammogram (CV) for the U(VI)/U(V) couple of a uranyl complex containing a multi-dentate chelating nitrogen/oxygen ligand (inset in figure). The couple is both chemically and electrochemically reversible. The CV in Figure 2b is that of [UO{sub 2}Cl{sub 4}]{sup 2-} in which the electrogenerated U(V) derivative is unstable yielding a chemically irreversible wave. For the compound giving rise to the CV in Figure 2a its electrochemical behavior in a conventional nonaqueous electrolyte medium is very similar to that obtained in the RTIL. While this result does not illustrate a distinct advantage for employing the RTIL solvent in this particular case, we believe it effectively demonstrates the ability of the RTIL to be utilized as a solvent/electrolyte medium for detailed electrochemical studies without severe limitations.

  3. 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 than ˜ 10 H2O/SO 3-, which is consistent with experimental observations. The sulfonate groups are also found to have influence on the proton hopping directions. The temperature and water content effects on the PT pathways are also investigated. The morphological effects on proton solvation and transport in hydrated Nafion are investigated, by using the SCI-MS-EVB method. Two of the most significant morphological models of Nafion, the lamellar model and the cylinder model, are selected. The two models exhibit distinct PT patterns, which result in different proton diffusion rates. In both models, the interaction between protons and the sulfonate groups are proven to be the key to determining PT behavior. The proton solvation structure change as a function of the distance between protons and sulfonate groups has been analyzed. It is found that the increase of water cylinder radius or water layer height leads to the presence of more protons around the sulfonate groups. Furthermore, at a lower hydration level, the increased amount of protons around the sulfonate groups consists of more Zundel-like structures, which is influenced by the distinct morphological structures of Nafion.

  4. 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

  5. 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.

  6. 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.

  7. 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...

  8. 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...

  9. Structure of [C4mpyr][NTf2] room-temperature ionic liquid at charged gold interfaces.

    PubMed

    Lauw, Yansen; Horne, Michael D; Rodopoulos, Theo; Lockett, Vera; Akgun, Bulent; Hamilton, William A; Nelson, Andrew R J

    2012-05-15

    The structure of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C(4)mpyr][NTf(2)]) room-temperature ionic liquid at an electrified gold interface was studied using neutron reflectometry, cyclic voltammetry, and differential capacitance measurements. Subtle differences were observed between the reflectivity data collected on a gold electrode at three different applied potentials. Detailed analysis of the fitted reflectivity data reveals an excess of [C(4)mpyr](+) at the interface, with the amount decreasing at increasingly positive potentials. A cation rich interface was found even at a positively charged electrode, which indicates a nonelectrostatic (specific) adsorption of [C(4)mpyr](+) onto the gold electrode. PMID:22515304

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

    NASA Astrophysics Data System (ADS)

    Ryan, David Martin

    The demonstration of a stable, reversible, alkali metal anode is an important step in the development of practical secondary batteries using room temperature chloroaluminate molten salts as electrolytes. Such melts are made by mixing 1-ethyl-3-methylimidazolium chloride (EMIC) with aluminum chloride, and can be Lewis buffered by adding LiCl or NaCl. It has been shown previously that protons added to a sodium chloride buffered melt as 1-ethyl-3-methyfimidazolium hydrogen dichloride (EMIHCl2) provide a more negative voltage window and nearly reversible deposition-stripping behavior for sodium. It is reported here that triethanolamine hydrogen chloride is effective in widening the voltage window, allows the plating and stripping of both lithium and sodium, and is stable in buffered EMIC/AlCl3 melts for months. It is suggested that deprotonation of one ethanolic group of triethanolamine HCl is responsible for the effect. The electrochemistry and UV-visible spectroscopy of several vanadium oxides have been examined in room temperature melts. By varying the mole ratio of the two components, Lewis basic, neutral and acidic melts were made. Most oxides have very low solubility: V2O4 and V2O3 are insoluble and V2O5 has a solubility limit less than 5 mM, but the solubilities of the salts NaVO 3, Na3VO4, and NH4VO3, VOCl 3 and VOF3 are significantly higher. The electrochemistry of V2O5, NaVO3, Na3VO4, NH4VO3, VOCl3 and VOF3 is similar in neutral and acidic melts. In the neutral melt each compound shows an irreversible reduction at about 0.45V vs. an Al wire reference electrode. In an acidic melt (mole fraction AlCl3 = 0.55) each of these compounds exhibit additional reduction peaks at more positive potentials. Coulometric and spectroscopic data for the 0.45V reduction suggest that mixed oxidation state polyvanadates may be formed. Controlled potential coulometry demonstrated that the reduction at 0.45V was the reduction of V(V) to V(IV) and the more positive reduction peaks 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.

  11. 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

  12. 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 244-601?m with pores of various size and shape of 0.02-100?m, 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

  13. Photodetachment, electron cooling, and recombination, in a series of neat aliphatic room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Molins i Domenech, Francesc; Healy, Andrew T.; Blank, David A.

    2015-08-01

    Transient absorption following photodetachment of a series of neat methyl-alkyl-pyrrolidinium bis(trifluoromethylsulfonyl)amides at 6.20 eV was measured with sub-picosecond time resolution in the visible and near-IR portions of the spectrum. This series spans the onset of structuring in the liquids in the form of polarity alternation. Excitation promotes the electron into a delocalized state with a very large reactive radius. Strong transient absorption is observed in the visible spectrum with a ˜700 fs lifetime, and much weaker, long-lived absorption is observed in the near-IR spectrum. Absorption in the visible is shown to be consistent with the hole, and absorption in the near-IR is assigned to the free solvated electron. Yield of free electrons is estimated at ˜4%, is insensitive to the size of the cation, and is determined in less than 1 ps. Solvation of free electrons depends strongly on the size of the cation and correlates well with the viscosity of the liquid. In addition to radiolytic stability of the aliphatic cations, ultrafast, efficient recombination of separated charge in NTf2 - based ionic liquids following photo-excitation near the band-gap may prevent subsequent reactive damage associated with anions.

  14. Photodetachment, electron cooling, and recombination, in a series of neat aliphatic room temperature ionic liquids.

    PubMed

    Molins i Domenech, Francesc; Healy, Andrew T; Blank, David A

    2015-08-14

    Transient absorption following photodetachment of a series of neat methyl-alkyl-pyrrolidinium bis(trifluoromethylsulfonyl)amides at 6.20 eV was measured with sub-picosecond time resolution in the visible and near-IR portions of the spectrum. This series spans the onset of structuring in the liquids in the form of polarity alternation. Excitation promotes the electron into a delocalized state with a very large reactive radius. Strong transient absorption is observed in the visible spectrum with a ∼700 fs lifetime, and much weaker, long-lived absorption is observed in the near-IR spectrum. Absorption in the visible is shown to be consistent with the hole, and absorption in the near-IR is assigned to the free solvated electron. Yield of free electrons is estimated at ∼4%, is insensitive to the size of the cation, and is determined in less than 1 ps. Solvation of free electrons depends strongly on the size of the cation and correlates well with the viscosity of the liquid. In addition to radiolytic stability of the aliphatic cations, ultrafast, efficient recombination of separated charge in NTf2 (-) based ionic liquids following photo-excitation near the band-gap may prevent subsequent reactive damage associated with anions. PMID:26277144

  15. 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

  16. 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 FeCl36H2O. 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 ?g.mL?1 to 0.2 ?g.mL?1 after the magnetic extraction by use of [3C6PC14][FeCl4]. PMID:21783320

  17. [Sb10Se10]2+, a heteronuclear polycyclic polycation from a room-temperature ionic liquid.

    PubMed

    Ahmed, Ejaz; Isaeva, Anna; Fiedler, Andy; Haft, Marcel; Ruck, Michael

    2011-06-01

    Reaction of antimony, selenium, and selenium(IV) chloride in the Lewis acidic ionic liquid [BMIM]Cl/AlCl(3) (BMIM: 1-n-butyl-3-methylimidazolium) at room temperature yielded air-sensitive black block-shaped crystals of [Sb(10)Se(10)][AlCl(4)](2). The triclinic unit cell (space group P1, a=947.85(2), b=957.79(2), c=1166.31(3) pm; α=103.622(1), β=110.318(1), γ=99.868(1)°; Z=1) contains the first mixed antimony/selenium polycation, [Sb(10)Se(10)](2+). The centrosymmetric polycyclic cation consists of two realgar-like [Sb(4)Se(4)] cages, which are connected through positively charged, three-bonded selenium atoms with a central [Sb(2)Se(2)] ring. Quantum chemical calculations predict semiconducting behavior of the compound and indicate primarily covalent bonding with varying ionic contribution within the [Sb(10)Se(10)](2+) polycation, while the interactions between the polycation and the [AlCl(4)](-) anions are predominantly ionic. The applicability of the Zintl concept to the chemical bonding in the heteronuclear polycation was evaluated by a thorough quantum chemical analysis. PMID:21547971

  18. 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

  19. Facile pretreatment of lignocellulosic biomass at high loadings in room temperature ionic liquids.

    PubMed

    Wu, Hong; Mora-Pale, Mauricio; Miao, Jianjun; Doherty, Thomas V; Linhardt, Robert J; Dordick, Jonathan S

    2011-12-01

    Ionic liquids (ILs) have emerged as attractive solvents for lignocellulosic biomass pretreatment in the production of biofuels and chemical feedstocks. However, the high cost of ILs is a key deterrent to their practical application. Here, we show that acetate based ILs are effective in dramatically reducing the recalcitrance of corn stover toward enzymatic polysaccharide hydrolysis even at loadings of biomass as high as 50% by weight. Under these conditions, the IL serves more as a pretreatment additive rather than a true solvent. Pretreatment of corn stover with 1-ethyl-3-methylimidizolium acetate ([Emim] [OAc]) at 125 ± 5°C for 1 h resulted in a dramatic reduction of cellulose crystallinity (up to 52%) and extraction of lignin (up to 44%). Enzymatic hydrolysis of the IL-treated biomass was performed with a common commercial cellulase/xylanase from Trichoderma reesei and a commercial β-glucosidase, and resulted in fermentable sugar yields of ∼80% for glucose and ∼50% for xylose at corn stover loadings up to 33% (w/w) and 55% and 34% for glucose and xylose, respectively, at 50% (w/w) biomass loading. Similar results were observed for the IL-facilitated pretreatment of switchgrass, poplar, and the highly recalcitrant hardwood, maple. At 4.8% (w/w) corn stover, [Emim][OAc] can be readily reused up to 10 times without removal of extracted components, such as lignin, with no effect on subsequent fermentable sugar yields. A significant reduction in the amount of IL combined with facile recycling has the potential to enable ILs to be used in large-scale biomass pretreatment. PMID:21769858

  20. 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.

  1. Electrochemical gas sensors based on paper-supported room-temperature ionic liquids for improved analysis of acid vapours.

    PubMed

    Toniolo, Rosanna; Dossi, Nicolò; Pizzariello, Andrea; Casagrande, Alice; Bontempelli, Gino

    2013-04-01

    A prototype of a fast-response task-specific amperometric gas sensor based on paper-supported room-temperature ionic liquids (RTILs) is proposed here for improved analysis of volatile acid species. It consists of a small filter paper foil soaked with a RTIL mixture containing an ionic liquid whose anion (acetate) displays a basic character, upon which three electrodes are screen printed by carbon ink profiting from a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs and of their easy immobilization into a porous and inexpensive supporting material such as paper. The performance of this device, used as a wall-jet amperometric detector for flow injection analyses of headspace samples in equilibrium with aqueous solutions at controlled concentrations, was evaluated for phenol and 1-butanethiol vapours which were adopted as model acid gaseous analytes. The results obtained showed that the quite high potentials required for the detection of these analytes are lowered significantly, thanks to the addition of the basic acetate RTIL. In such a way, overlap with the medium discharge is avoided, and the possible adverse effect of interfering species is minimised. The sensor performance was quite satisfactory (detection limits, ca. 0.3 μM; dynamic range, ca. 1-200 μM, both referred to solution concentrations; correlation coefficients in the range 0.993-0.997; repeatability, ± 6% RSD; long-term stability, 9%); thus suggesting the possible use of this device for manifold applications. PMID:23232956

  2. Room-temperature ionic liquid-amine solutions: tunable solvents for efficient and reversible capture of CO{sub 2}

    SciTech Connect

    Dean Camper; Jason E. Bara; Douglas L. Gin; Richard D. Noble

    2008-11-05

    Solutions of room-temperature ionic liquids (RTILs) and commercially available amines were found to be effective for the capture of CO{sub 2} as carbamate salts. RTIL solutions containing 50 mol % (16% v/v) monoethanolamine (MEA) are capable of rapid and reversible capture of 1 mol of CO{sub 2} per 2 moles MEA to give an insoluble MEA-carbamate precipitate that helps to drive the capture reaction (as opposed to aqueous amine systems). Diethanolamine (DEA) can also be used in the same manner for CO{sub 2} capture in RTILs containing a pendant hydroxyl group. The captured CO{sub 2} in the resulting RTIL-carbamate salt mixtures can be readily released by either heating and/or subjecting them to reduced pressure. Using this unprecedented and industrially attractive mixing approach, the desirable properties of RTILs (i.e., nonvolatility, enhancedCO{sub 2} solubility, lower heat capacities) can be combined with the performance of amines for CO{sub 2} capture without the use of specially designed, functionalized 'task-specific' ionic liquids. By mixing RTILs with commercial amines, reactive solvents with a wide range of amine loading levels can be tailored to capture CO{sub 2} in a variety of conditions and processes. These RTIL-amine solutions behave similarly to their water-based counterparts but may offer many advantages, including increased energy efficiency, compared to current aqueous amine technologies.

  3. 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

  4. 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

  5. Highly reversible lithium metal secondary battery using a room temperature ionic liquid/lithium salt mixture and a surface-coated cathode active material.

    PubMed

    Seki, Shiro; Kobayashi, Yo; Miyashiro, Hajime; Ohno, Yasutaka; Usami, Akira; Mita, Yuichi; Watanabe, Masayoshi; Terada, Nobuyuki

    2006-02-01

    For the purpose of realizing high-voltage, high-capacity, long-life and safe rechargeable batteries, a lithium secondary battery that uses high-voltage stable ZrO2-coated LiCoO2 cathode powder and a nonvolatile high-safety room temperature ionic liquid was fabricated. PMID:16432577

  6. 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...

  7. 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

  8. Direct electrochemistry and electrocatalysis of heme proteins entrapped in agarose hydrogel films in room-temperature ionic liquids.

    PubMed

    Wang, Sheng-Fu; Chen, Ting; Zhang, Zhi-Ling; Shen, Xin-Cheng; Lu, Zhe-Xue; Pang, Dai-Wen; Wong, Kwok-Yin

    2005-09-27

    The electrochemistry and electrocatalysis of a number of heme proteins entrapped in agarose hydrogel films in the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]) have been investigated. UV-vis and FTIR spectroscopy show that the heme proteins retain their native structure in agarose film. The uniform distribution of hemoglobin in agarose-dimethylformamide film was demonstrated by atomic force microscopy. Cyclic voltammetry shows that direct electron transfer between the heme proteins and glassy carbon electrode is quasi-reversible in [bmim][PF(6)]. The redox potentials for hemoglobin, myoglobin, horseradish peroxidase, cytochrome c, and catalase were found to be more negative than those in aqueous solution. The charge-transfer coefficient and the apparent electron-transfer rate constant for these heme proteins in [bmim][PF(6)] were calculated from the peak-to-peak separation as a function of scan rate. The heme proteins catalyze the electroreduction of trichloroacetic acid and tert-butyl hydroperoxide in [bmim][PF(6)]. The kinetic parameter I(max) (maximum current at saturation concentration of substrate) and the apparent K(m) (Michaelis-Menten constant) for the electrocatalytic reactions were evaluated. PMID:16171360

  9. 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

  10. A novel nitromethane biosensor based on biocompatible conductive redox graphene-chitosan/hemoglobin/graphene/room temperature ionic liquid matrix.

    PubMed

    Wang, Lu; Zhang, Xiuhua; Xiong, Huayu; Wang, Shengfu

    2010-11-15

    A novel amperometric biosensor for nitromethane (CH(3)NO(2)) based on immobilization of graphene (GR), chitosan (CS), hemoglobin (Hb) and room temperature ionic liquid (IL) on a glassy carbon electrode (GCE) was developed for the first time. The surface morphologies of a set of representative membranes were characterized by means of scanning electron microscopy (SEM). The electrochemical performance of the biosensor was evaluated by cyclic voltammetry (CV) and chronoamperometry. A pair of stable and well-defined redox peaks of Hb with a formal potential of -0.240 V was observed at the GR-CS/Hb/GR/IL/GCE. The effects of phosphate buffer pH, scan rate, and temperature on the biosensor were investigated to provide optimum analytical performance. Moreover, several electrochemical parameters, e.g., the heterogeneous electron transfer rate constant (k(s)), were calculated in detail. The presence of both GR and IL not only dramatically facilitated the electron transfer of Hb, but also greatly enhanced electrocatalytic activity towards CH(3)NO(2). The apparent Michaelis-Menten constant was down to 0.16 μM, indicating that the biosensor possessed high affinity to CH(3)NO(2). Besides this, the proposed biosensor exhibited fast amperometric response (<5s), low detection limit (6.0 × 10(-10)M), and excellent long-time storage stability for the determination of CH(3)NO(2). PMID:20833016

  11. Kinetic Effect on Pressure-Induced Phase Transitions of Room Temperature Ionic Liquid, 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate.

    PubMed

    Li, Haining; Wang, Zheng; Chen, Liucheng; Wu, Jie; Huang, Haijun; Yang, Kun; Wang, Yongqiang; Su, Lei; Yang, Guoqiang

    2015-11-01

    Room temperature ionic liquids (RTILs) have intriguing high-pressure phase behavior, and investigation of how pressure affects phase transitions of RTILs might yield interesting results. We here present kinetically driven phase transitions of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Emim][CF3SO3]) at different rates of ∼0.3 and ∼1.2 GPa/h up to ∼5 GPa. Two crystalline phases formed at ∼1.3 and ∼1.7 GPa with increasing pressure at lower compression rate of ∼0.3 GPa/h; however, the amorphous phase solidified with superpressurized glass above ∼3.3 GPa at higher compression rate of ∼1.2 GPa/h. Notably, crystal polymorphism is discussed in view of the conformational isomerism of [Emim](+) cation and an unknown cation conformer is observed. These facts indicate that kinetic effect on pressure-induced phase transitions of [Emim][CF3SO3] might be dependent on compression rate, which needs to be considered as a non-negligible factor for phase transitions of RTILs under high pressure. PMID:26465251

  12. 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

  13. Liquid-liquid extraction of Pu(IV), U(VI) and Am(III) using malonamide in room temperature ionic liquid as diluent.

    PubMed

    Rout, Alok; Venkatesan, K A; Srinivasan, T G; Vasudeva Rao, P R

    2012-06-30

    The extraction behavior of U(VI), Pu(IV) and Am(III) from nitric acid medium by a solution of N,N-dimethyl-N,N-dioctyl-2-(2-hexyloxyethyl)malonamide (DMDOHEMA) in the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C(4)mimNTf(2)), was studied. The distribution ratio of these actinides in DMDOHEMA/C(4)mimNTf(2) was measured as a function of various parameters such as the concentration of nitric acid, DMDOHEMA, NTf(2)(-), alkyl chain length of ionic liquid. The extraction of actinides in the absence of DMDOHEMA was insignificant and the distribution ratio achieved in conjunction with C(4)mimNTf(2), was remarkable. The separation factor of U(VI) and Pu(IV) achieved with the use of DMDOHEMA, ionic liquid was compared with Am(III) and other fission products. The stoichiometry of the metal-solvate was determined to be 1:2 for U(VI) and Pu(IV) and 1:3 for Am(III). PMID:22541638

  14. 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

  15. 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.

  16. Effect of nitrate, perchlorate, and water on uranyl(VI) speciation in a room-temperature ionic liquid: a spectroscopic investigation.

    PubMed

    Pasilis, Sofie P; Blumenfeld, Alexander

    2011-09-01

    Room-temperature ionic liquids form potentially important solvents in novel nuclear waste reprocessing methods, and the solvation, speciation, and complexation behaviors of lanthanides and actinides in these solvents are of great current interest. In the study reported here, the coordination environment of uranyl(VI) in solutions of the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf(2)N]) containing perchlorate, tetrabutylammonium nitrate, and water was investigated using Raman, ATR-FTIR, and NMR spectroscopies in order to better understand the role played in uranyl(VI) solution chemistry in room-temperature ionic liquids by water and other small, weakly complexing ligands. The (2)H NMR chemical shift for water in a solution of uranyl perchlorate hexahydrate in [EMIM][Tf(2)N] appears at 6.52 ppm, indicating that water is coordinated to uranyl(VI). A broad ν(OH) stretching mode at 3370 cm(-1) in the ATR-FTIR spectrum shows that this coordinated water is engaged in hydrogen bonding with water molecules in a second coordination sphere. A significant upfield shift in the (2)H NMR signal for water and the appearance of distinct ν(as)(HOH) (at 3630 cm(-1)) and ν(s)(HOH) (at 3560 cm(-1)) vibrational bands in the ATR-FTIR spectra show that coordinated water is displaced by nitrate upon formation of the UO(2)(NO(3))(2) and UO(2)(NO(3))(3)(-) complexes. The Raman spectra indicate that perchlorate complexed to uranyl(VI) is also displaced by nitrate. Our results indicate that perchlorate and water, though weakly complexing ligands, do have a role in uranyl(VI) speciation in room-temperature ionic liquids and that Raman, infrared, and NMR spectroscopies are valuable additions to the suite of tools currently used to study the chemical behavior of uranyl(VI)-ligand complexes in these solvents. PMID:21786806

  17. 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 nanomaterials such as nanoporous CDC nanopowders, vertically aligned carbon nanotube arrays, and single wall carbon nanotube aerogels, were synthesized and used as electrodes, alongside RTIL electrolytes with systematically varying ion sizes and compositions. While electrode/electrolyte development can take place along parallel lines, both must be properly matched to the device's ultimate operating conditions and specific application. The resulting devices exhibit good performance characteristics, and the best temperature range of any electrochemical storage device to date.

  18. Sum frequency generation spectroscopy of dicyanamide based room-temperature ionic liquids. Orientation of the cation and the anion at the gas-liquid interface.

    PubMed

    Aliaga, Cesar; Baldelli, Steven

    2007-08-23

    The orientation of the cation and the anion of room-temperature ionic liquids using sum frequency generation vibrational spectroscopy is reported. The ionic liquids are based on butyl-methyl imidazolium [BMIM]+ and hexyl-tributyl ammonium [N6444]+ together with dicyanamide [DCA]- as the anion. The tilt angle of the C3 axis of the methyl group from the alkyl chain in the cations was found to vary from 52 degrees to 80 degrees as a function of the distribution width sigma (which ranges from 0 degrees to 30 degrees with respect to the surface normal) for [BMIM][DCA] and similarly for [N6444][DCA]. The orientation of the C2 axis in the dicyanamide anion as a function of the twist angle phi, varied between 46 degrees and 90 degrees for [BMIM][DCA] and from 53 degrees to 90 degrees for [N6444][DCA]. These results suggest the presence of both ionic species at the gas-liquid interface and help describe the behavior of a simple inorganic anion at the surface. PMID:17661511

  19. Electrochemical behavior of biocatalytical composite based on heme-proteins, didodecyldimethylammonium bromide and room-temperature ionic liquid.

    PubMed

    Xu, Yanxia; Hu, Chengguo; Hu, Shengshui

    2010-03-17

    A novel biocompatible composite film based on a water-insoluble surfactant, didodecyldimethylammonium bromide (DDAB), and a hydrophobic room-temperature ionic liquid (RTIL), 1-hexyl-3-methyl-imidazolium hexafluorophosphate (HIMIMPF(6)), for the immobilization of biocatalytical proteins was reported. Differential scanning calorimetry (DSC) showed that the DDAB-HIMIMPF(6) composite film has higher thermal stability than the DDAB film alone. SEM images indicated that different microstructures existed between the DDAB film and the composite film, indicating the interaction between DDAB and RTILs. This composite can be used as the immobilization matrix of proteins and other biomacromolecules. Heme-proteins, including hemoglobin (Hb), myoglobin (Mb) and horseradish peroxidase (HRP), were used as model proteins for studying the electrochemical behaviors of the resulting biocatalytical composite films. In the case of Hb, a pair of well-defined quasi-reversible redox peaks was obtained when the composite film containing Hb was modified on a glassy carbon electrode. The formal potential (E degrees '), the surface coverage (Gamma(*)) and the electron transfer rate constant (k(s)) were calculated as -0.308V, 1.32x10(-11)molcm(-2) and 11.642s(-1), respectively. While, these parameters for Hb on DDAB films alone were -0.309V, 7.20x10(-12)molcm(-2) and 2.748s(-1), respectively. Therefore, the composite are more suitable for the direct electron transfer between Hb than DDAB alone. The native conformation and bioactivity of Hb adsorbed on the composite film was proved to be maintained, reflected by the unchanged ultraviolet-visible (UV-vis) as well as the catalytic activity toward hydrogen peroxide (H(2)O(2)) and nitric oxide (NO) compared with the free Hb molecules. Furthermore, Hb on the composite film are more sensitive for the detection of hydrogen peroxide (H(2)O(2)) and nitric oxide (NO) than that on DDAB film alone. The linear range of H(2)O(2) on Hb/DDAB-RTILs/GC electrode is from 0.5 to 57.5microM with linear regression equations I(microA)=0.149+0.00904C(microM), while, the linear range of H(2)O(2) on Hb/DDAB/GC electrode is from 0.5 to 57.5microM with linear regression equations I(microA)=0.0938+0.00553C(microM). For NO, its linear range on Hb/DDAB-RTILs/GC electrode is from 1.8 to 21.6microM with linear regression equations I(microA)=0.0937+0.0232C(microM). But its linear range on Hb/DDAB/GC electrode is from 1.8 to 21.6microM with linear regression equations I(microA)=0.0285+0.0167C(microM). Similar results were observed for Mb and HRP in the DDAB-HIMIMPF(6) composite film. PMID:20172091

  20. Relationships between center atom species (N, P) and ionic conductivity, viscosity, density, self-diffusion coefficient of quaternary cation room-temperature ionic liquids.

    PubMed

    Seki, Shiro; Hayamizu, Kikuko; Tsuzuki, Seiji; Fujii, Kenta; Umebayashi, Yasuhiro; Mitsugi, Takushi; Kobayashi, Takeshi; Ohno, Yasutaka; Kobayashi, Yo; Mita, Yuichi; Miyashiro, Hajime; Ishiguro, Shin-ichi

    2009-05-14

    The physicochemical properties (ionic conductivity, viscosity, density, and self-diffusion coefficient) of tri-n-ethylpentylphosphonium bis(trifluoromethanesulfonyl)amide (TEPP-TFSA) ionic liquid were compared with those of tri-n-ethylpentylammonium bis(trifluoromethanesulfonyl)amide (TEPA-TFSA). Compared with the TEPA-TFSA ionic liquid, the density and viscosity of the phosphorus ionic liquid are lower, although the ionic conductivity and self-diffusion coefficient are higher. The molar conductivities were compared for the values obtained by the electrochemical impedance method (electrochemical conductivity) and the calculated from the pulsed-gradient spin-echo nuclear magnetic resonance method (diffusive conductivity). The comparison shows that active ionic ratios of the TEPP-TFSA ionic liquid were smaller than those of the TEPA-TFSA ionic liquid in the whole temperature, regardless of the lower viscosity of the TEPP-TFSA ionic liquid, and results with high precision were obtained using Walden's law. PMID:19421555

  1. 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.

  2. Decompression-induced crystal polymorphism in a room-temperature ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate.

    PubMed

    Yoshimura, Yukihiro; Abe, Hiroshi; Imai, Yusuke; Takekiyo, Takahiro; Hamaya, Nozomu

    2013-03-21

    We explore the phase behavior of room-temperature ionic liquids (RTILs) compressed under high pressure to determine whether they crystallize or hold a liquid state. RTILs have attractive supercooling properties compared with ordinary molecular liquids, which easily become a glassy state without crystallizing at ambient pressure. Thus, phase behavior under extreme stress, such as pressure, might yield interesting results. Here, we show that N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate ([DEME][BF4]) could be crystallized upon compression, but it usually formed a superpressed liquid. Alternatively, unusual crystallization could be induced by releasing the pressure on the superpressed liquid. Notably, crystal polymorphism was observed in the decompression process. These facts along with visual observations indicate the possibility of [DEME][BF4] serving as a superpressurized glass. Our findings may facilitate the development of a new range of applications for RTILs that have undergone high-pressure recrystallization. PMID:23427814

  3. Usefulness of reversed-phase HPLC enriched with room temperature imidazolium based ionic liquids for lipophilicity determination of the newly synthesized analgesic active urea derivatives.

    PubMed

    Flieger, Jolanta; Czajkowska-Żelazko, Anna; Rządkowska, Marzena; Szacoń, Elżbieta; Matosiuk, Dariusz

    2012-07-01

    Lipophilicity of several novel analgesic active 1-(1-arylimidazolidyn-2-ylidyn)-3-arylalkyl urea derivatives has been estimated by the use of chromatographic method. The investigated compounds were analyzed by reversed-phase high performance liquid chromatography (RP-HPLC) using mixtures of methanol or acetonitrile and water with addition of imidazolium based room temperature ionic liquids varying in an anion chaotropicity as the mobile phases. The relationships between log k values vs. concentration of organic solvent was used for determination of the log k(w) values by extrapolation technique. The partition coefficients (log P) values were calculated by means of the Pallas 3.1.1.2. and Spartan 10.0 softwares and further correlated with log k(w) measured experimentally in classical organic-aqueous eluent system and systems modified with ionic liquids addition. It was found that log k(w) values measured in eluent system modified with butyl-methyl imidazoilum chloride correlate the best with the logarithm of partition coefficient calculated by Pallas software (log P(calc.)). Furthermore, it was found that the examined compounds form H-bonding with imidazoilum cation of modifiers improving the chromatographic peak parameters (the symmetry factor, the theoretical plates number) especially when ionic liquid's anion was more chaotropic. Amphiphilic ionic liquid possessing longer alkyl chain substituent (OMIM BF(4)) can be considered as a new cationic surfactant. Micellar conditions improved separation selectivity of chloro- and methoxy substituted derivatives. PMID:22445825

  4. Carprofen-imprinted monolith prepared by reversible addition-fragmentation chain transfer polymerization in room temperature ionic liquids.

    PubMed

    Ban, Lu; Han, Xu; Wang, Xian-Hua; Huang, Yan-Ping; Liu, Zhao-Sheng

    2013-10-01

    To obtain fast separation, ionic liquids were used as porogens first in combination with reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare a new type of molecularly imprinted polymer (MIP) monolith. The imprinted monolithic column was synthesized using a mixture of carprofen (template), 4-vinylpyridine, ethylene glycol dimethacrylate, [BMIM]BF4, and chain transfer agent (CTA). Some polymerization factors, such as template-monomer molar ratio, the degree of crosslinking, the composition of the porogen, and the content of CTA, on the column efficiency and imprinting effect of the resulting MIP monolith were systematically investigated. Affinity screening of structurally similar compounds with the template can be achieved in 200 s on the MIP monolith due to high column efficiency (up to 12,070 plates/m) and good column permeability. Recognition mechanism of the imprinted monolith was also investigated. PMID:23942589

  5. 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

  6. 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.

  7. 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.

  8. Small volume laboratory on a chip measurements incorporating the quartz crystal microbalance to measure the viscosity-density product of room temperature ionic liquids.

    PubMed

    Doy, N; McHale, G; Newton, M I; Hardacre, C; Ge, R; Macinnes, J M; Kuvshinov, D; Allen, R W

    2010-01-01

    A microfluidic glass chip system incorporating a quartz crystal microbalance (QCM) to measure the square root of the viscosity-density product of room temperature ionic liquids (RTILs) is presented. The QCM covers a central recess on a glass chip, with a seal formed by tightly clamping from above outside the sensing region. The change in resonant frequency of the QCM allows for the determination of the square root viscosity-density product of RTILs to a limit of approximately 10 kg m(-2) s(-0.5). This method has reduced the sample size needed for characterization from 1.5 ml to only 30 mul and allows the measurement to be made in an enclosed system. PMID:20644676

  9. Small volume laboratory on a chip measurements incorporating the quartz crystal microbalance to measure the viscosity-density product of room temperature ionic liquids

    PubMed Central

    Doy, N.; McHale, G.; Newton, M. I.; Hardacre, C.; Ge, R.; MacInnes, J. M.; Kuvshinov, D.; Allen, R. W.

    2010-01-01

    A microfluidic glass chip system incorporating a quartz crystal microbalance (QCM) to measure the square root of the viscosity-density product of room temperature ionic liquids (RTILs) is presented. The QCM covers a central recess on a glass chip, with a seal formed by tightly clamping from above outside the sensing region. The change in resonant frequency of the QCM allows for the determination of the square root viscosity-density product of RTILs to a limit of ∼10 kg m−2 s−0.5. This method has reduced the sample size needed for characterization from 1.5 ml to only 30 μl and allows the measurement to be made in an enclosed system. PMID:20644676

  10. 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

  11. 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

  12. Ultrafast solvation response in room temperature ionic liquids: Possible origin and importance of the collective and the nearest neighbour solvent modes

    NASA Astrophysics Data System (ADS)

    Daschakraborty, Snehasis; Biswas, Ranjit

    2012-09-01

    Recent three-pulse photon echo peak shift (3PEPS) measurements [M. Muramatsu, Y. Nagasawa, and H. Miyasaka, J. Phys. Chem. A 115, 3886 (2011)], 10.1021/jp108282v with several room temperature ionic liquids (RTILs) have revealed multi-exponential dynamics with ultrafast solvation timescale in the range, 20 < τ1/fs < 250, for both imidazolium and phosphonium RTILs. This is striking for two reasons: (i) the timescale is much faster than those reported by the dynamic Stokes shift (DSS) experiments [S. Arzhantsev, H. Jin, G. A. Baker, and M. Maroncelli, J. Phys. Chem. B 111, 4978 (2007)], 10.1021/jp067273m and (ii) sub-hundered femtosecond solvation response in phosphonium ionic liquids is reported for the first time. Here, we present a mode coupling theory based calculation where such ultrafast solvation in 3PEPS measurements has been visualized to originate from the nearest neighbour solute-solvent interaction. Consideration of Lennard-Jones interaction for the nearest neighbour solute-solvent non-dipolar interaction leads to biphasic dynamics with a predicted ultrafast time constant in the ˜100-250 fs range, followed by a slower one similar to that reported by the 3PEPS measurements. In addition, the calculated fast time constants and amplitudes are found to be in general agreement with those from computer simulations. Different microscopic mechanisms for ultrafast solvation response measured by the 3PEPS and DSS experiments have been proposed and relative contributions of the collective and nearest neighbour solvent modes investigated. Relation between the single particle rotation and ultrafast polar solvation in these RTILs has been explored. Our analyses suggest 3PEPS and DSS experiments are probably sensitive to different components of the total solvation energy relaxation of a laser-excited dye in a given ionic liquid. Several predictions have also been made, which may be re-examined via suitable experiments.

  13. 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.

  14. 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-ended portion of the survey data, an analysis of organic chemistry textbooks was created. Books were analyzed for number and types of problems, number of example problems, and number of problems containing answers in the back of the book. The analysis of the thirteen books revealed there was a statistically significant difference between the books in number and types of problems. This work will reveal the findings of the analysis.

  15. Superacidic or not…? Synthesis, characterisation, and acidity of the room-temperature ionic liquid [C(CH3)3]+  [Al2Br7]-.

    PubMed

    Scholz, Franziska; Himmel, Daniel; Scherer, Harald; Krossing, Ingo

    2013-01-01

    The room-temperature ionic liquid (RT-IL) [C(CH(3))(3)](+)[Al(2)Br(7)](-) (m.p. 2 °C) was generated by bromide abstraction from tert-butyl bromide with the Lewis acid aluminum bromide in the absence of solvent. The crystal structure of the tert-butyl cation salt was determined by X-ray diffraction. NMR, IR, and Raman spectroscopy, as well as quantum-chemical and thermodynamic calculations, confirm the composition of this RT-IL. Thus, one may consider this RT-IL to be a readily accessible (and on a large scale) cationic Brønsted acid (protonated isobutene) with the potential for further reactivity. Based on the new absolute Brønsted acidity scale, we calculated an absolute pH(abs) value of 171 for liquid bulk [C(CH(3))(3)](+)[Al(2)Br(7)](-). This value is about as acidic as 100 % sulfuric acid (pH(abs) = 171) and, thus, on the edge of superacidity. PMID:23180742

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. Structure and orientation of the imidazolium cation at the room-temperature ionic liquid/SiO2 interface measured by sum-frequency vibrational spectroscopy.

    PubMed

    Rollins, Julie B; Fitchett, Brian D; Conboy, John C

    2007-05-10

    In this study, we have examined both the effect of alkyl chain length and anion composition on the 1-alkyl-3-methylimidazolium (C(n)mim, n = 4, 6, 8, 10, and 12) structure and orientation at the room-temperature ionic liquid (RTIL)/SiO(2) interface by sum-frequency vibrational spectroscopy (SFVS). Four different anions were investigated in this study: tetrafluoroborate (BF(4)), hexafluorophosphate (PF(6)), bis(trifluoromethylsulfonyl)imide (BMSI), and bis(pentafluoroethylsulfonyl)imide (BETI). It was found that the alkyl chain in BMSI and BETI RTILs showed a decrease in gauche defects with an increase in chain length, whereas the alkyl chains of the BF(4) and PF(6) RTILs have virtually no gauche defects regardless of chain length. The tilt of the alkyl chain lies predominantly perpendicular to the surface for all the RTILs examined. A strong correlation between the HCCH vs tilt angle and alkyl chain length was observed; as the alkyl chain is lengthened the HCCH vs lies more perpendicular to the SiO(2) surface. The results of this study suggest that the length of the alkyl chain dictates to a large degree the orientation of the imidazolium cation at the surface, regardless of anion composition. To a lesser extent, the HCCH vs tilt of the imidazolium ring of the cation also appears to be correlated to the surface charge density of the SiO(2). As the SiO(2) surface charge density becomes more negative the HCCH vs tilt angle lies more parallel to the surface. PMID:17441750

  3. Synthesis and development of ordered, phase-separated, room-temperature ionic liquid-based AB and ABC block copolymers for gas separation applications

    NASA Astrophysics Data System (ADS)

    Wiesenauer, Erin F.

    CO2 capture process development is an economically and environmentally important challenge, as concerns over greenhouse gas emissions continue to receive worldwide attention. Many applications require the separation of CO 2 from other light gases such as N2, CH4, and H2 and a number of technologies have been developed to perform such separations. While current membrane technology offers an economical, easy to operate and scale-up solution, polymeric membranes cannot withstand high temperatures and aggressive chemical environments, and they often exhibit an unfavorable tradeoff between permeability and selectivity. Room-temperature ionic-liquids (RTILs) are very attractive as next-generation CO2-selective separation media and their development into polymerized membranes combat these challenges. Furthermore, polymers that can self-assemble into nanostructured, phase-separated morphologies (e.g., block copolymers, BCPs) have a direct effect on gas transport as materials morphology can influence molecular diffusion and membrane transport performance. In this thesis, nanophase-separated, RTIL-based AB and ABC di- and tri-BCPs were prepared via the sequential, living ring-opening metathesis polymerization (ROMP) of an IL-based monomer and one or more mutually immiscible co-monomers. This novel type of ion-containing BCP system forms various ordered nanostructures in the melt state via primary and secondary structure control. Monomer design and control of block composition, sequence, and overall polymer lengths were found to directly affect the ordered polymer assembly. Supported, composite membranes of these new BCPs were successfully fabricated, and the effect of BCP composition and nanostructure on CO2/light gas transport properties was studied. These nanostructured IL-based BCPs represent innovative polymer architectures and show great potential CO2/light gas membrane separation applications.

  4. Room-Temperature Liquid Crystal Blue Phases

    NASA Astrophysics Data System (ADS)

    Taushanoff, Stefanie; van Le, Khoa; Twieg, Robert; Jakli, Antal

    2009-03-01

    The ``blue phases'' of a highly chiral liquid crystal are defect-studded structures of double-twist cylinders that are laced together. The three phases, BPI*, BPII* and BPIII* differ only in the packing of the double-twist cylinders. Until recently, blue phases were of limited practical use because they appeared for only a very narrow temperature range. Mixtures that show BPI* and BPII* phases for wide temperature ranges at or around room temperature are now available [1]. Relatively wide temperature BPIII (the blue fog) phase so far was available only at very high temperatures [2]. Here we present mixtures with room-temperature wide range BPIII* phase and compare the ability of chiral dopants to form the different blue phases in a base nematic mixture. PDLC films cast with blue-phase material are also examined.[3pt] [1] H. Coles and M. Pivnenko, Nature 2005 436-18 997-1000 [0pt] [2] C. V. Yelamaggad, I. S. Shashikala, G. Liao, D.S. Shankar Rao, S. K. Prasad , Q. Li A. Jakli, Chem. Mater Comm, 2006, 18, 6100-6102

  5. 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

  6. An efficient ultrasound assisted approach for the impregnation of room temperature ionic liquid onto Dowex 1×8 resin matrix and its application toward the enhanced adsorption of chromium (VI).

    PubMed

    Kalidhasan, S; Kumar, A Santhana Krishna; Rajesh, Vidya; Rajesh, N

    2012-04-30

    The work discussed in this paper is based on the utilization of ultrasound in conjunction with an ionic liquid (Aliquat 336) impregnated Dowex 1×8 resin for the effective adsorption of chromium. Ionic liquids are known for their selectivity toward metal extraction and ultrasonic medium offers efficient energy transfer for impregnating the ionic liquid in the resin matrix. The molecular interaction between the ionic liquid impregnated resin and chromium was studied through various physicochemical and spectroscopic techniques. The influence of various analytical parameters on the adsorption of Cr(VI) such as pH, adsorbent dosage, temperature and interference of foreign ions was studied in detail. Chromium (VI) was quantitatively adsorbed in the pH range of 3.5-4, with a high adsorption capacity of 230.9 mg g(-1) in conformity with the Langmuir isotherm model. The study of thermodynamic parameters showed that the adsorption process is exothermic and spontaneous. The adsorbent could be regenerated using 1 mol L(-1) HCl-0.28 mol L(-1) ascorbic acid mixture. Chromium could be effectively detoxified from an industrial effluent and finally the developed method was validated with the analysis of a certified reference material (BCR-715). The obtained results indicated that the ultrasonic assisted impregnation of the room temperature ionic liquid significantly enhances and improves the removal efficiency of Cr(VI). PMID:22365143

  7. 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

  8. Effect of Temperature on the Physico-Chemical Properties of a Room Temperature Ionic Liquid (1-Methyl-3-pentylimidazolium Hexafluorophosphate) with Polyethylene Glycol Oligomer

    PubMed Central

    Wu, Tzi-Yi; Chen, Bor-Kuan; Hao, Lin; Peng, Yu-Chun; Sun, I-Wen

    2011-01-01

    A systematic study of the effect of composition on the thermo-physical properties of the binary mixtures of 1-methyl-3-pentyl imidazolium hexafluorophosphate [MPI][PF6] with poly(ethylene glycol) (PEG) [Mw = 400] is presented. The excess molar volume, refractive index deviation, viscosity deviation, and surface tension deviation values were calculated from these experimental density, ρ, refractive index, n, viscosity, η, and surface tension, γ, over the whole concentration range, respectively. The excess molar volumes are negative and continue to become increasingly negative with increasing temperature; whereas the viscosity and surface tension deviation are negative and become less negative with increasing temperature. The surface thermodynamic functions, such as surface entropy, enthalpy, as well as standard molar entropy, Parachor, and molar enthalpy of vaporization for pure ionic liquid, have been derived from the temperature dependence of the surface tension values. PMID:21731460

  9. Influence of γ-radiation on room-temperature ionic liquid [bmim][PF 6] in the presence of nitric acid

    NASA Astrophysics Data System (ADS)

    Yuan, Liyong; Peng, Jing; Zhai, Maolin; Li, Jiuqiang; Wei, Genshuan

    2009-07-01

    Stability of ionic liquid 1-methyl-3-butylimidazolium hexafluorophosphate ([bmim][PF 6]) in the presence of nitric acid (HNO 3) was investigated under γ-radiation. It was found that incorporating HNO 3 into [bmim][PF 6] obviously inhibits the radiation-induced darkening of [bmim][PF 6] due to the oxidizability of HNO 3. More detailed UV-vis analysis reveals linear decrease of light absorbance of irradiated [bmim][PF 6]/HNO 3 with increasing concentration of HNO 3 to 2 mol L -1, which is consistent with the color evolution observed by the naked eye. FTIR and NMR measurements indicates that HNO 3 slightly accelerates the radiolysis of [bmim][PF 6] at high dose (550 kGy), the amount of nonvolatile radiolysis products, however, is less than 1 mol%.

  10. 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

  11. 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.

  12. Synthesis of ionic liquids

    SciTech Connect

    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.

  13. Thermally stable AgI quantum-dot-based room-temperature fast ionic conductors.

    PubMed

    Xu, Biao; Wang, Xun

    2011-12-16

    AgI quantum dot (QD)-based room-temperature fast ionic conductors are prepared via an aqueous route. New phase behavior and good performance are found in this material. This is a prototype of quantum dot-ionics. PMID:22038711

  14. 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

  15. 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 counterions of uranyl or introducing extra anions. PMID:25629464

  16. Stretchable microelectrode array using room-temperature liquid alloy interconnects

    NASA Astrophysics Data System (ADS)

    Wei, P.; Taylor, R.; Ding, Z.; Chung, C.; Abilez, O. J.; Higgs, G.; Pruitt, B. L.; Ziaie, B.

    2011-05-01

    In this paper, we present a stretchable microelectrode array for studying cell behavior under mechanical strain. The electrode array consists of gold-plated nail-head pins (250 µm tip diameter) or tungsten micro-wires (25.4 µm in diameter) inserted into a polydimethylsiloxane (PDMS) platform (25.4 × 25.4 mm2). Stretchable interconnects to the outside were provided by fusible indium-alloy-filled microchannels. The alloy is liquid at room temperature, thus providing the necessary stretchability and electrical conductivity. The electrode platform can withstand strains of up to 40% and repeated (100 times) strains of up to 35% did not cause any failure in the electrodes or the PDMS substrate. We confirmed biocompatibility of short-term culture, and using the gold pin device, we demonstrated electric field pacing of adult murine heart cells. Further, using the tungsten microelectrode device, we successfully measured depolarizations of differentiated murine heart cells from embryoid body clusters.

  17. 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

  18. How Is Diffusion of Neutral and Charged Tracers Related to the Structure and Dynamics of a Room-Temperature Ionic Liquid? Large Deviations from Stokes-Einstein Behavior Explained.

    PubMed

    Araque, Juan C; Yadav, Sharad K; Shadeck, Michael; Maroncelli, Mark; Margulis, Claudio J

    2015-06-11

    The deviations from Stokes-Einstein hydrodynamics of small solutes are more pronounced in ionic liquids than in conventional solvents (J. Phys. Chem. B 2013 117 (39), 11697). Small neutral solutes diffuse much faster than expected, whereas small charged solutes diffuse much slower. This article attempts to establish a link between the local friction experienced by tracer solutes and the polar/apolar structure of ionic liquids. We find that small neutral solutes probe locally "stiff" (mostly charged, high electrostriction) regions and locally "soft" (mostly apolar, low electrostriction) regions. These regions of high and low friction are associated with cage and jump regimes. Enhanced neutral tracer mobility in the low friction regions associated with the cationic apolar component has an important bearing on the large positive deviations from Stokes-Einstein behavior. In contrast, diminished charged tracer mobility involves long caging dynamics separated by jump events often triggered by the loss and recovery of counterions. PMID:25811753

  19. Phosphonium-based ionic liquids and uses

    DOEpatents

    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.

  20. 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.

  1. 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.

  2. ELECTROCHEMICAL STUDIES OF HEMIN IN IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ionic liquids (ILs), room temperature liquid organic salts, have gained prominence as alternative media for volatile organic solvents. Recent studies have shown that some enzymes tolerate ILs and have catalytic activities comparable to those obtained in molecular organic solvents. We have investig...

  3. Electrochemical transistors with ionic liquids for enzymatic sensing.

    PubMed

    Yang, Sang Yoon; Cicoira, Fabio; Byrne, Robert; Benito-Lopez, Fernando; Diamond, Dermot; Owens, Róisín M; Malliaras, George G

    2010-11-14

    We report an enzymatic sensor based on an organic electrochemical transistor that uses a room temperature ionic liquid as an integral part of its structure and as an immobilization medium for the enzyme and the mediator. PMID:20871879

  4. 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.

  5. 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 can be used to interpolate predictions for low surface tension cryogenic liquids only when pore diameters are based on room temperature bubble point tests and not SEM analysis as presently implemented.

  6. 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.

  7. 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)

  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. 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

  10. Fullerene Incorporation into SWNTs in Liquid-Phase at Room Temperature

    NASA Astrophysics Data System (ADS)

    Yudasaka, Masako; Ajima, Kumiko; Suenaga, Kazu; Ichihashi, Toshinari; Hashimoto, Ayako; Iijima, Sumio

    2004-03-01

    We are interested in the incorporation of materials, especially organic molecules, within carbon nanotubes for biological applications such as drug delivery. A critical problem for such applications is that gas-phase incorporation methods, useful for introducing C60 into SWNTs, cannot be applied to many biologically interesting molecules because such molecules are often thermally unstable and can neither be evaporated nor sublimed. We previously proposed a method of nanoextraction which enabled C60 incorporation into single-wall carbon nanotubes (SWNTs) and nanohorns (SWNHs) in the liquid phase. Further refinement of this method enabled instantaneous (within a few seconds) incorporation of C60 into SWNTs and SWNHs at room temperature (1). This instantaneous incorporation works when the affinity balances of the molecules, SWNTs, and solvent satisfy a certain relationship. The details are discussed in the presentation. (1) M. Yudasaka et al. Chem. Phys. Lett. 380 (2003) 42.

  11. 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.

  12. 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.

  13. 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

  14. 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

  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 novel method for hydrogen production from liquid ethanol/water at room temperature.

    PubMed

    Sekine, Yasushi; Urasaki, Kohei; Asai, Shinjiro; Matsukata, Masahiko; Kikuchi, Eiichi; Kado, Shigeru

    2005-01-01

    We demonstrated that non-catalytic ethanol steam reforming proceeds efficiently and selectively without coking at the conditions of room temperature and atmospheric pressure using low-energy pulsed (LEP) discharge in combination with carbon fiber electrodes. PMID:15614378

  17. A room-temperature processed parylene-patterned helical ionic polymer-metal composite spring actuator with selectable active region

    NASA Astrophysics Data System (ADS)

    Feng, Guo-Hua; Zhan, Zhen-Hua

    2014-04-01

    This paper presents a novel helical ionic polymer metal composite (IPMC) spring actuator. A room-temperature fabrication process is developed to selectively grow in situ nickel metal electrode on a coiled Nafion strip, which is patterned with parylene as a masking layer to delineate the inactive region. This method allows the helical spring actuator to be shaped in a near-constant temperature environment and minimizes the residual stress effect on the Nafion polymer, compared to other processes using thermal treatment. The developed process ensures that short-circuiting never occurs between the outer and inner electrodes of the actuator, and the active region can be designed via parylene patterning. The motion of the fabricated spring actuator is measured, and the maximal displacement reaches 1 mm at the endpoint of the spring under a 0.1 Hz 6 V square wave actuation. A microtensile experiment is performed for characterizing the stress and strain relation. The resulting Young’s moduli of the Nafion and fabricated IPMC strips are 183 and 227 MPa, respectively. Analysis based on Castigliano’s theorem is executed to derive equations related to the moment, force output, strain energy, and displacement of an arbitrary point of the fabricated spring actuator. Results show the produced moment, force, and strain energy of the operated spring actuator are in the level of 1.5 μN m, 300 mN, and 20-100 μJ, respectively.

  18. 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 experiments. Overall, the combined experimental measurements and simulations indicate that hydrogen storage based on enhanced solubility in nano-confined liquids is unlikely to meet the storage densities required for practical use. Only low gravimetric capacities of < 0.5 wt% were achieved. More importantly, solvent filled scaffolds had lower volumetric capacities than corresponding empty scaffolds. Nevertheless, several of the composites measured did show significant (>~ 5x) enhanced hydrogen solubility relative to bulk solvent solubility, when the hydrogen capacity was attributed only to dissolution in the confined solvent. However, when the hydrogen capacity was compared to an empty scaffold that is known to store hydrogen by surface adsorption on the scaffold walls, including the solvent always reduced the hydrogen capacity. For the best composites, this reduction relative to an empty scaffold was ~30%; for the worst it was ~90%. The highest capacities were obtained with the largest solvent molecules and with scaffolds containing 3- dimensionally confined pore geometries. The simulations suggested that the capacity of the composites originated from hydrogen adsorption on the scaffold pore walls at sites not occupied by solvent molecules. Although liquid solvent filled the pores, not all of the adsorption sites on the pore walls were occupied due to restricted motion of the solvent molecules within the confined pore space.

  19. 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-elastomer interfaces are described.

  20. 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

  1. Wide range room temperature electroclinic liquid crystal mixture with large induced tilt and very small layer contraction

    NASA Astrophysics Data System (ADS)

    Debnath, Asim; Sinha, Debashis; Mandal, Pradip Kumar

    2016-03-01

    Optical polarizing microscopy, synchrotron X-ray scattering, and electro-optic studies in the SmA* phase of a formulated wide range room temperature liquid crystal mixture indicate a large electric field induced optical tilt up to 23.5° along with a very small contraction of smectic layers. Applied field primarily lifts the zero-field degeneracy of the azimuthal order of the molecules in smectic layers resulting in small layer contraction.

  2. 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.

  3. 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.

  4. 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.

  5. Ionic liquids behave as dilute electrolyte solutions.

    PubMed

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

    2013-06-11

    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

  6. 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

  7. 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(trihexyl)phosphonium dicyanamide as the RTIL. It was determined that it has good absorption properties for methanol and α-pinene, is thermally stable, and is relatively easy to synthesize. It has a density of 0.89 g/mL at 20°C and a molecular weight of 549.9 g/mol. Trials were conducted with a small absorption system and a larger absorption system. Methanol, formaldehyde, and other HAPs were absorbed well, nearly 100%. Acetaldehyde was difficult to capture. Total VOC capture, while satisfactory on methanol and α-pinene in a lab system, was less than expected in the field, 60-80%. The inability to capture the broad spectrum of total organics is likely due to difficulties in cleaning them from the ionic liquid rather than the ability of the ionic liquid to absorb. It’s likely that a commercial system could be constructed to remove 90 to 100% of the gas contaminates. Selecting the correct ionic liquid would be key to this. Absorption may not be the main selection criterion, but rather how easily the ionic liquid can be cleaned is very important. The ionic liquid absorption system might work very well in a system with a limited spectrum of pollutants, such as a paint spray line, where there are not very high molecular weight, non volatile, compounds in the exhaust.

  8. 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

    2016-05-01

    A laboratory-assembled surfactant-assisted pressurized liquid extraction system at room temperature was used for the extraction of glycyrrhizin (GLY) inRadix 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 inRadix glycyrrhizaeusing 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

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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

  14. Liquid polystyrene: a room-temperature photocurable soft lithography compatible pour-and-cure-type polystyrene.

    PubMed

    Nargang, Tobias M; Brockmann, Lara; Nikolov, Pavel Mitkov; Schild, Dieter; Helmer, Dorothea; Keller, Nico; Sachsenheimer, Kai; Wilhelm, Elisabeth; Pires, Leonardo; Dirschka, Marian; Kolew, Alexander; Schneider, Marc; Worgull, Matthias; Giselbrecht, Stefan; Neumann, Christiane; Rapp, Bastian E

    2014-08-01

    Materials matter in microfluidics. Since the introduction of soft lithography as a prototyping technique and polydimethylsiloxane (PDMS) as material of choice the microfluidics community has settled with using this material almost exclusively. However, for many applications PDMS is not an ideal material given its limited solvent resistance and hydrophobicity which makes it especially disadvantageous for certain cell-based assays. For these applications polystyrene (PS) would be a better choice. PS has been used in biology research and analytics for decades and numerous protocols have been developed and optimized for it. However, PS has not found widespread use in microfluidics mainly because, being a thermoplastic material, it is typically structured using industrial polymer replication techniques. This makes PS unsuitable for prototyping. In this paper, we introduce a new structuring method for PS which is compatible with soft lithography prototyping. We develop a liquid PS prepolymer which we term as "Liquid Polystyrene" (liqPS). liqPS is a viscous free-flowing liquid which can be cured by visible light exposure using soft replication templates, e.g., made from PDMS. Using liqPS prototyping microfluidic systems in PS is as easy as prototyping microfluidic systems in PDMS. We demonstrate that cured liqPS is (chemically and physically) identical to commercial PS. Comparative studies on mouse fibroblasts L929 showed that liqPS cannot be distinguished from commercial PS in such experiments. Researchers can develop and optimize microfluidic structures using liqPS and soft lithography. Once the device is to be commercialized it can be manufactured using scalable industrial polymer replication techniques in PS--the material is the same in both cases. Therefore, liqPS effectively closes the gap between "microfluidic prototyping" and "industrial microfluidics" by providing a common material. PMID:24887072

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

    DOEpatents

    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.

  16. 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

  17. 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

  18. 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).

  19. 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

  20. 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.

  1. Electrochemical behavior of ferrocene in ionic liquid media.

    PubMed

    Nagy, Lívia; Gyetvai, Gergely; Kollár, László; Nagy, Géza

    2006-11-30

    Chemistry and applicability of ionic liquids (IL), - organic salts with low melting point - are in the focus of interest today. The ILs with melting point below room temperature are expected to be good solvents. Their applicability in organic synthetic work, in separation processes as well as in electrochemistry is very promising. In the work reported here the voltammetric behavior of ferrocene in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM+ PF6-) ionic liquid has been investigated. Conventional size and micro platinum and carbon electrodes were employed in CV and in chronoamperometric measurements. Karl Fischer method was used for the determination of water content of the solvent. Voltammetric measurements without addition of background electrolyte could be carried out in (BMIM+ PF6-) ionic liquid. A broad potential window could be used. Concentration dependence of the electrochemically determined diffusion coefficient of the ferrocene was observed. PMID:16650899

  2. 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

  3. 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.

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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 1H NMR and 13C 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.

  6. 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.

  7. 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.

  8. 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.

  9. Morphology-enhanced conductivity in dry ionic liquids.

    PubMed

    Erbaş, Aykut; de la Cruz, Monica Olvera

    2016-03-01

    Ionic liquids exhibit fascinating nanoscale morphological phases and are promising materials for energy storage applications. Liquid crystalline order emerges in ionic liquids with specific chemical structures. Here, we investigate the phase behaviour and related ionic conductivities of dry ionic liquids, using extensive molecular dynamics simulations. Temperature dependence, properties of polymeric tail and excluded volume symmetry of the amphiphilic ionic liquid molecules are investigated in large scale systems with both short and long-range Coulomb interactions. Our results suggest that by adjusting stiffness and steric interactions of the amphiphilic molecules, lamellar or 3D continuous phases result in these molecular salts. The resulting phases are composed of ion rich and ion pure domains. In 3D phases, ion rich clusters form ionic channels and have significant effects on the conductive properties of the observed nano-phases. If there is no excluded-volume asymmetry along the molecules, mostly lamellar phases with anisotropic conductivities emerge. If the steric interactions become asymmetric, lamellar phases are replaced by complex 3D continuous phases. Within the temperature ranges for which morphological phases are observed, conductivities exhibit low-temperature maxima in accord with experiments on ionic liquid crystals. Stiffer molecules increase the high-conductivity interval and strengthen temperature-resistance of morphological phases. Increasing the steric interactions of cation leads to higher conductivities. Moreover, at low monomeric volume fractions and at low temperatures, cavities are observed in the nano-phases of flexible ionic liquids. We also demonstrate that, in the absence of electrostatic interactions, the morphology is distorted. Our findings inspire new design principles for room temperature ionic liquids and help explain previously-reported experimental data. PMID:26862598

  10. 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

  11. 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.

  12. 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.

  13. 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 amine interactions. The hypothesis is that the performance at the elevated temperatures could be improved by allowing a facilitated transport mechanism to become dominant. Several amine-based ionic liquids were tested on the cross-linked nylon support. It was found that using the amine-based ionic liquid did improve selectivity and permeability at higher temperature. The hypothesis was confirmed, and it was determined that the type of amine used also played a role in facilitated transport. Given the appropriate aminated ionic liquid with the cross-linked nylon support, it is possible to have a membrane capable of separating CO2 at IGCC conditions. With this being the case, the research has expanded to include separation of other constituents besides CO2 (CO, H2S, etc.) and if they play a role in membrane poisoning or degradation. This communication will discuss the operation of the recently fabricated ionic liquid membranes and the impact of gaseous components other than CO2 on their performance and stability.

  14. Determination of the polarities of some ionic liquids using 2-nitrocyclohexanone as the probe.

    PubMed

    Angelini, Guido; Chiappe, Cinzia; De Maria, Paolo; Fontana, Antonella; Gasparrini, Francesco; Pieraccini, Daniela; Pierini, Marco; Siani, Gabriella

    2005-09-30

    Solute-solvent interactions on the keto-enol tautomerism of 2-nitrocyclohexanone in several organic solvents and room-temperature ionic liquids (RTILs) have been analyzed in terms of multiparameter equations. Permittivity and cohesive pressure values of the RTILs, unavailable by direct measurements, have been derived. PMID:16277347

  15. Polarization versus temperature in pyridinium ionic liquids.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2014-12-01

    Electronic polarization and charge transfer effects play a crucial role in thermodynamic, structural, and transport properties of room-temperature ionic liquids (RTILs). These nonadditive interactions constitute a useful tool for tuning physical chemical behavior of RTILs. Polarization and charge transfer generally decay as temperature increases, although their presence should be expected over an entire condensed state temperature range. For the first time, we use three popular pyridinium-based RTILs to investigate temperature dependence of electronic polarization in RTILs, based on a nonperiodic electronic density description for a cation-anion pair. Atom-centered density matrix propagation molecular dynamics, supplemented by a weak coupling to an external bath, is used to simulate the temperature impact on system properties. We show that, quite surprisingly, nonadditivity in the cation-anion interactions changes negligibly between 300 and 900 K, while the average dipole moment increases due to thermal fluctuations of geometries. Our results contribute to the fundamental understanding of electronic effects in the condensed phase of ionic systems and foster progress in physical chemistry and engineering. PMID:25387327

  16. 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.

  17. 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.

  18. 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...

  19. Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

    NASA Astrophysics Data System (ADS)

    Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

    2012-09-01

    The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

  20. 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.

  1. 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.

  2. PEROXIDASE ACTIVITY IN IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Only a few enzymes have been examined in ionic liquids (ILs) to date. Initial results suggest that at least some enzymes tolerate ILs at least as well as conventional molecular solvents. Our work further explores the possibility that ILs provide a suitable (i.e., non-denaturing, non-inhibitory) en...

  3. 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.

  4. Transport properties, optical response and slow dynamics of ionic liquids

    NASA Astrophysics Data System (ADS)

    Hu, Zhonghan

    In this thesis, we report on our studies of the transport properties, optical response and slow dynamical nature of novel room temperature ionic liquids. Using computer simulations we have demonstrated that the diffusive dynamics of these systems is in many ways analogous to that of other glassy or supercooled liquids. These solvents show non-Gaussian rotational and translational diffusion which have a temporal extent on the order of nanoseconds at room temperature. Our study of their response upon application of an external mechanical perturbation shows that even for systems with a box length as large as 0.03 microns the viscosities computed from perturbation wavenumbers compatible with this box size have not yet reached the hydrodynamic limit. We found these systems to behave in a non-Newtonian fashion and we also observe a clear break down of linear response theory on the nano- or sub-micrometer scale. Upon photoexcitation of an organic probe with lifetime shorter than the reorganization timescale in these ionic liquids, (which is quite long on the order of several nanoseconds at least), the emission spectrum is absorption wavelength dependent. Our computer simulations rationalized this observation in terms of local solvent environment around individual subensemble probe members. Excitation of different solute molecules in the liquid gives rise to site-specific optical responses. We revealed that the origin of this excitation wavelength dependence is the existence of persistent excited-state environments that do not get solvent averaged on a time scale relevant to fluorescence. The computed time resolved fluorescence spectra show that the full loss of correlation between absorption and emission frequencies for probes in room temperature ionic liquids occur on a time scale of nanoseconds. One of the most interesting features of ionic liquids is their uncommonly large range of dynamical time scales which in turn makes some of their properties to be quite different from that of most other conventional solvents. We hope that our understanding of these phenomena will be useful in the future in the development of tools to harness their potential to control the outcome of chemical and photo-chemical reactions.

  5. Synthesis of new solid polymer electrolyte and actuator based on PEDOT/NBR/ionic liquid

    NASA Astrophysics Data System (ADS)

    Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

    2006-03-01

    The conducting polymer actuator was presented. The solid polymer electrolyte based on nitrile rubber (NBR) activated with different ionic liquids was prepared. The three different grades of NBR films were synthesized by emulsion polymerization with different amount of acrylonitrile, 23, 35, and 40 mol. %, respectively. The effect of acrylonitrile content on the ionic conductivity and dielectric constant of solid polymer electrolytes was characterized. A conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique, and room temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X [where X= BF 4 -, PF 6 -, (CF 3SO II) IIN -], were absorbed into the composite film. The effects of the anion size of the ionic liquids on the displacement of the actuator were examined. The displacement increased with increasing the anion-size of the ionic liquids.

  6. Surface tension of ionic liquids and ionic liquid solutions.

    PubMed

    Tariq, Mohammad; Freire, Mara G; Saramago, Benilde; Coutinho, João A P; Lopes, José N Canongia; Rebelo, Luís Paulo N

    2012-01-21

    Some of the most active scientific research fronts of the past decade are centered on ionic liquids. These fluids present characteristic surface behavior and distinctive trends of their surface tension versus temperature. One way to explore and understand their unique nature is to study their surface properties. This critical review analyses most of the surface tension data reported between 2001 and 2010 (187 references). PMID:21811714

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    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.

  9. Ionic Liquids in Biomass Processing

    NASA Astrophysics Data System (ADS)

    Tan, Suzie Su Yin; Macfarlane, Douglas R.

    Ionic liquids have been studied for their special solvent properties in a wide range of processes, including reactions involving carbohydrates such as cellulose and glucose. Biomass is a widely available and renewable resource that is likely to become an economically viable source of starting materials for chemical and fuel production, especially with the price of petroleum set to increase as supplies are diminished. Biopolymers such as cellulose, hemicellulose and lignin may be converted to useful products, either by direct functionalisation of the polymers or depolymerisation to monomers, followed by microbial or chemical conversion to useful chemicals. Major barriers to the effective conversion of biomass currently include the high crystallinity of cellulose, high reactivity of carbohydrates and lignin, insolubility of cellulose in conventional solvents, as well as heterogeneity in the native lignocellulosic materials and in lignin itself. This combination of factors often results in highly heterogeneous depolymerisation products, which make efficient separation difficult. Thus the extraction, depolymerisation and conversion of biopolymers will require novel reaction systems in order to be both economically attractive and environmentally benign. The solubility of biopolymers in ionic liquids is a major advantage of their use, allowing homogeneous reaction conditions, and this has stimulated a growing research effort in this field. This review examines current research involving the use of ionic liquids in biomass reactions, with perspectives on how it relates to green chemistry, economic viability, and conventional biomass processes.

  10. 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

  11. 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.

  12. Density-viscosity product of small-volume ionic liquid samples using quartz crystal impedance analysis.

    PubMed

    McHale, Glen; Hardacre, Chris; Ge, Rile; Doy, Nicola; Allen, Ray W K; MacInnes, Jordan M; Bown, Mark R; Newton, Michael I

    2008-08-01

    Quartz crystal impedance analysis has been developed as a technique to assess whether room-temperature ionic liquids are Newtonian fluids and as a small-volume method for determining the values of their viscosity-density product, rho eta. Changes in the impedance spectrum of a 5-MHz fundamental frequency quartz crystal induced by a water-miscible room-temperature ionic liquid, 1-butyl-3-methylimiclazolium trifluoromethylsulfonate ([C4mim][OTf]), were measured. From coupled frequency shift and bandwidth changes as the concentration was varied from 0 to 100% ionic liquid, it was determined that this liquid provided a Newtonian response. A second water-immiscible ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4mim][NTf2], with concentration varied using methanol, was tested and also found to provide a Newtonian response. In both cases, the values of the square root of the viscosity-density product deduced from the small-volume quartz crystal technique were consistent with those measured using a viscometer and density meter. The third harmonic of the crystal was found to provide the closest agreement between the two measurement methods; the pure ionic liquids had the largest difference of approximately 10%. In addition, 18 pure ionic liquids were tested, and for 11 of these, good-quality frequency shift and bandwidth data were obtained; these 12 all had a Newtonian response. The frequency shift of the third harmonic was found to vary linearly with square root of viscosity-density product of the pure ionic liquids up to a value of square root(rho eta) approximately 18 kg m(-2) s(-1/2), but with a slope 10% smaller than that predicted by the Kanazawa and Gordon equation. It is envisaged that the quartz crystal technique could be used in a high-throughput microfluidic system for characterizing ionic liquids. PMID:18611039

  13. 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.

  14. COMPARISON OF PEROXIDASE ACTIVITIES OF HEMIN, CYTOCHROME C AND MICROPEROXIDASE-11 IN MOLECULAR SOLVENTS AND IMIDAZOLIUM-BASED IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The ability of ferriprotoporphyrin(IX) chloride (hemin), microperoxidase-11 (MP-11), and cytochrome c (cyt-c) to oxidize guaiacol (2-methoxyphenol) was examined in the room-temperature ionic liquids (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and the hexafluorophosphates of 1-...

  15. Mono- and multi-layer adsorption of an ionic liquid on Au(110).

    PubMed

    Foulston, Richard; Gangopadhyay, Subhashis; Chiutu, Cristina; Moriarty, Philip; Jones, Robert G

    2012-05-01

    Ultraviolet photoelectron spectroscopy (UPS), work function measurements, low energy electron diffraction (LEED) and scanning tunnelling microscopy (STM) have been used to study the adsorption and desorption of 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [C(2)C(1)Im][Tf(2)N], on the (1×2) clean surface reconstruction of Au(110) in the temperature range 100-674 K. The ionic liquid adsorbed without decomposition, and desorbed without leaving any residue on the surface. For adsorption at room temperature a monolayer of strongly bound ionic liquid was formed with four interface states visible in UP spectra. STM at 100 K showed that the monolayer consisted of well-ordered rows of adsorbed ionic liquid aligned parallel to the close packed rows of surface gold atoms (the [110] direction) with a separation of ×2 (the same as the clean surface reconstruction) between the rows in the orthogonal [001] direction. Multilayer adsorption at room temperature occurred by droplet formation followed by smoothing of the droplets to a layered morphology with time. Heating caused multilayer desorption at temperatures in the 363-383 K range, followed by partial monolayer desorption at 548 K to produce a Au(110)-(1×3) reconstructed surface with sub-monolayer domains of ionic liquid. Desorption of the remaining ionic liquid at 600 K caused the gold surface to reconstruct back to the clean (1×2) reconstruction. PMID:22441396

  16. 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.

  17. Surface orientation in ionic liquids

    NASA Astrophysics Data System (ADS)

    Law, George; Watson, Philip R.

    2001-09-01

    New surface tension data supports models of surface orientations previously derived from direct recoil spectrometry (DRS) data for the cations of 1-alkyl-3-methylimidazolium ionic liquids. For shorter-chain hexafluorophosphate compounds the favored average orientation appears to be one where the cation is oriented vertically with the N atoms uppermost, but the alkyl substituents do not protrude out of the surface. For longer chains or for compounds containing the smaller tetrafluoroborate anion the surface tension and DRS data are consistent with a shift to an average orientation embodying a rotation that moves the methyl group towards the surface.

  18. 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.

  19. 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

  20. 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.

  1. Electronic functions of solid-to-liquid interfaces of organic semiconductor crystals and ionic liquid

    NASA Astrophysics Data System (ADS)

    Takeya, J.

    2008-10-01

    The environment of surface electrons at 'solid-to-liquid' interfaces is somewhat extreme, subjected to intense local electric fields or harsh chemical pressures that high-density ionic charge or polarization of mobile molecules create. In this proceedings, we argue functions of electronic carriers generated at the surface of organic semiconductor crystals in response to the local electric fields in the very vicinity of the interface to ionic liquid. The ionic liquids (ILs), or room temperature molten salts, are gaining considerable interest in the recent decade at the prospect of nonvolatile 'green solvents', with the development of chemically stable and nontoxic compounds. Moreover, such materials are also applied to electrolytes for lithium ion batteries and electric double-layer (EDL) capacitors. Our present solid-to-liquid interfaces of rubrene single crystals and ionic liquids work as fast-switching organic field-effect transistors (OFETs) with the highest transconductance, i.e. the most efficient response of the output current to the input voltage, among the OFETs ever built.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. New frontiers in materials science opened by ionic liquids.

    PubMed

    Torimoto, Tsukasa; Tsuda, Tetsuya; Okazaki, Ken-ichi; Kuwabata, Susumu

    2010-03-19

    Ionic liquids (ILs) including ambient-temperature molten salts, which exist in the liquid state even at room temperature, have a long research history. However, their applications were once limited because ILs were considered as highly moisture-sensitive solvents that should be handled in a glove box. After the first synthesis of moisture-stable ILs in 1992, their unique physicochemical properties became known in all scientific fields. ILs are composed solely of ions and exhibit several specific liquid-like properties, e.g., some ILs enable dissolution of insoluble bio-related materials and the use as tailor-made lubricants in industrial applications under extreme physicochemical conditions. Hybridization of ILs and other materials provides quasi-solid materials, which can be used to fabricate highly functional devices. ILs are also used as reaction media for electrochemical and chemical synthesis of nanomaterials. In addition, the negligible vapor pressure of ILs allows the fabrication of electrochemical devices that are operated under ambient conditions, and many liquid-vacuum technologies, such as X-ray photoelectron spectroscopy (XPS) analysis of liquids, electron microscopy of liquids, and sputtering and physical vapor deposition onto liquids. In this article, we review recent studies on ILs that are employed as functional advanced materials, advanced mediums for materials production, and components for preparing highly functional materials. PMID:20437507

  9. 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.

  10. Liquid metal alloy ion source based metal ion injection into a room-temperature electron beam ion sourcea)

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

    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 Au60 +. The setup, the charge breeding technique, breeding efficiencies as well as acceptance and emittance studies are presented.

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

    PubMed

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

    2012-02-01

    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(60 +). The setup, the charge breeding technique, breeding efficiencies as well as acceptance and emittance studies are presented. PMID:22380207

  12. 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.

  13. 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

  14. 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.

  15. Silver halide fiber-based evanescent-wave liquid droplet sensing with room temperature mid-infrared quantum cascade lasers

    NASA Astrophysics Data System (ADS)

    Chen, J. Z.; Liu, Z.; Gmachl, C. F.; Sivco, D. L.

    2005-08-01

    Quantum cascade lasers and unclad silver halide fibers were used to assemble mid-infrared fiber-optics evanescent-wave sensors suitable to measure the chemical composition of liquid droplets. The laser wavelengths were chosen to be in the regions which offer the largest absorption contrast between constituents inside the mixture droplets. A pseudo-Beer-Lambert law fits well with the experimental data. Using a 300μm diameter fiber with a 25 mm immersion length, the signal to noise ratios correspond to 1 vol.% for α-tocophenol in squalane and 2 vol.% for acetone in aqueous solution for laser wavenumbers of 1208 cm-1 and 1363 cm-1, respectively.

  16. Thermal properties of ionic systems near the liquid-liquid critical point

    NASA Astrophysics Data System (ADS)

    Méndez-Castro, Pablo; Troncoso, Jacobo; Pérez-Sánchez, Germán; Peleteiro, José; Romaní, Luis

    2011-12-01

    Isobaric heat capacity per unit volume, Cp, and excess molar enthalpy, hE, were determined in the vicinity of the critical point for a set of binary systems formed by an ionic liquid and a molecular solvent. Moreover, and, since critical composition had to be accurately determined, liquid-liquid equilibrium curves were also obtained using a calorimetric method. The systems were selected with a view on representing, near room temperature, examples from clearly solvophobic to clearly coulombic behavior, which traditionally was related with the electric permittivity of the solvent. The chosen molecular compounds are: ethanol, 1-butanol, 1-hexanol, 1,3-dichloropropane, and diethylcarbonate, whereas ionic liquids are formed by imidazolium-based cations and tetrafluoroborate or bis-(trifluromethylsulfonyl)amide anions. The results reveal that solvophobic critical behavior—systems with molecular solvents of high dielectric permittivity—is very similar to that found for molecular binary systems. However, coulombic systems—those with low permittivity molecular solvents—show strong deviations from the results usually found for these magnitudes near the liquid-liquid phase transition. They present an extremely small critical anomaly in Cp—several orders of magnitude lower than those typically obtained for binary mixtures—and extremely low hE—for one system even negative, fact not observed, up to date, for any liquid-liquid transition in the nearness of an upper critical solution temperature.

  17. Nonlinear polarization of ionic liquids: theory, simulations, experiments

    NASA Astrophysics Data System (ADS)

    Kornyshev, Alexei

    2010-03-01

    Room temperature ionic liquids (RTILs) composed of large, often asymmetric, organic cations and simple or complex inorganic or organic anions do not freeze at ambient temperatures. Their rediscovery some 15 years ago is widely accepted as a ``green revolution'' in chemistry, offering an unlimited number of ``designer'' solvents for chemical and photochemical reactions, homogeneous catalysis, lubrication, and solvent-free electrolytes for energy generation and storage. As electrolytes they are non-volatile, some can sustain without decomposition up to 6 times higher voltages than aqueous electrolytes, and many are environmentally friendly. The studies of RTILs and their applications have reached a critical stage. So many of them can be synthesized - about a thousand are known already - their mixtures can further provide ``unlimited'' number of combinations! Thus, establishing some general laws that could direct the best choice of a RTIL for a given application became crucial; guidance is expected from theory and modelling. But for a physical theory, RTILs comprise a peculiar and complex class of media, the description of which lies at the frontier line of condensed matter theoretical physics: dense room temperature ionic plasmas with ``super-strong'' Coulomb correlations, which behave like glasses at short time-scale, but like viscous liquids at long-time scale. This talk will introduce RTILs to physicists and overview the current understanding of the nonlinear response of RTILs to electric field. It will focus on the theory, simulations, and experimental characterisation of the structure and nonlinear capacitance of the electrical double layer at a charged electrode. It will also discuss pros and contras of supercapacitor applications of RTILs.

  18. Thermoreversible Ion Gels by Block Copolymer Self-assembly in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    He, Yiyong; Lodge, Timothy

    2007-03-01

    Ion gels, formed by swelling a polymer network with ionic liquids, have been shown to be promising candidates towards highly conductive solid-state electrolytes. Through the self-assembly of triblock copolymers in room-temperature ionic liquids, transparent ion gels could be obtained. Due to the low copolymer concentration, the ionic conductivity of the resulting ion gels is only modestly affected by the triblock copolymer network. By further selecting thermo-responsive end blocks in the triblock copolymers, thermoreversible ion gels were developed. The gelation behavior, ionic conductivity, rheological properties, and microstructure of the ion gels were investigated in detail. The results presented here suggest that triblock copolymer gelation is a promising way to develop highly conductive ion gels.

  19. 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

  20. 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

  1. Analysis of cationic structure in some room-temperature molten fluorides and dependence of their ionic conductivity and viscosity on hydrofluoric acid concentration.

    PubMed

    Isogai, Tomohiro; Nakai, Takaaki; Inoue, Hidemi; Nakanishi, Kenta; Kohara, Shinji; Saito, Morihiro; Inaba, Minoru; Tasaka, Akimasa

    2011-08-11

    To understand the ionic and nonionic species in (CH(3))(4)NF·mHF, (CH(3))(3)N·mHF, (C(2)H(5))(4)NF·mHF, and (C(2)H(5))(3)N·mHF melts, the structures of these melts were investigated by infrared spectroscopy, NMR, and high-energy X-ray diffraction. Infrared spectra revealed that three kinds of fluorohydrogenate anions, (FH)(n)F(-) (n = 1, 2, and 3), and molecular hydrofluoric acid (HF) are present in every melt. Ionic conductivity and viscosity of these melts were measured and correlated with their cationic structure. The ionic conductivity of the R(4)N(+)-systems was higher than that of corresponding R(3)NH(+)-systems because a strong N-H···F(HF)(n) interaction prevents the motion of R(3)NH(+) cations in the R(3)N·mHF melts. (CH(3))(4)N(+) and (CH(3))(3)NH(+) cations gave higher ionic conductivity than (C(2)H(5))(4)N(+) and (C(2)H(5))(3)NH(+) cations, respectively, because the ionic radii of former cations were smaller than those of latter. It was concluded that these effects on ionic conductivity can be explained by the cationic structure and the concentration of molecular HF in the melts. PMID:21714521

  2. 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.

  3. Ionic Conductivity of Nanostructured Block Copolymer and Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan L.; Virgili, Justin M.; Segalman, Rachel A.

    2010-03-01

    Block copolymer and ionic liquid mixtures are of interest for creating ionically conductive, thermally stable, and nanostructured membranes. For mixtures of poly(styrene-b-2-vinylpyridine) (S2VP) and the ionic liquid bis(trifluoromethanesulfonyl)imide ([Im][TFSI]), nanostructured ion-conducting domains are formed due to [Im][TFSI] selectively residing in the P2VP domains of the block copolymer. The dependence of ionic conductivity on temperature, ionic liquid loading, and volume fraction of PS in the neat block copolymer was investigated for membranes with the matrix phase being P2VP/[Im][TFSI]. It was determined that the temperature dependence of conductivity follows the Vogel-Tamman-Fulcher equation, with the activation energy determined by the ratio of [Im][TFSI] to 2VP monomers. The overall weight fraction of [Im][TFSI] in the mixtures, however, is the dominating factor determining conductivity, regardless of PS volume fraction. The insight gained from this work will be important for further investigation into the effect on the ion transport properties of ionic liquids when confined to minority nanostructured domains.

  4. Electrolyte-gated polymer thin film transistors making use of ionic liquids and ionic liquid-solvent mixtures

    NASA Astrophysics Data System (ADS)

    Sayago, Jonathan; Meng, Xiang; Quenneville, Francis; Liang, Shuang; Bourbeau, Étienne; Soavi, Francesca; Cicoira, Fabio; Santato, Clara

    2015-03-01

    Electrolyte-Gated (EG) transistors, making use of electrolytes as the gating medium, are interesting for their low operation voltage. Furthermore, EG polymer transistors offer the advantage of solution processing, low cost, and mechanical flexibility. Despite the intense research activity in EG transistors, clear guidelines to correlate the properties of the materials used for the transistor channel and electrolytes with the doping effectiveness of the transistor channel are yet to be clearly established. Here, we investigate the use of room temperature ionic liquids (RTILs) based on the [TFSI] anion (namely, [EMIM][TFSI], [BMIM][TFSI], and [PYR14][TFSI]), to gate transistors making use of MEH-PPV as the channel material. Morphological studies of MEH-PPV and RTIL films showed a certain degree of segregation between the two components. All the EG transistors featured clear drain-source current modulations at voltages below 1 V. Polar solvent additives as propylene carbonate were used to improve the transistor response time.

  5. Polymer--Ionic liquid Electrolytes for Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Ketabi, Sanaz

    Polymer electrolyte, comprised of ionic conductors, polymer matrix, and additives, is one of the key components that control the performance of solid flexible electrochemical capacitors (ECs). Ionic liquids (ILs) are highly promising ionic conductors for next generation polymer electrolytes due to their excellent electrochemical and thermal stability. Fluorinated ILs are the most commonly applied in polymer-IL electrolytes. Although possessing high conductivity, these ILs have low environmental favorability. The aim of this work was to develop environmentally benign polymer-ILs for both electrochemical double layer capacitors (EDLCs) and pseudocapacitors, and to provide insights into the influence of constituent materials on the ion conduction mechanism and the structural stability of the polymer-IL electrolytes. Solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and 1-ethyl-3-methylimidazolium hydrogen sulfate (EMIHSO4) were investigated for ECs. The material system was optimized to achieve the two criteria for high performance polymer-ILs: high ionic conductivity and highly amorphous structure. Thermal and structural analyses revealed that EMIHSO4 acted as an ionic conductor and a plasticizer that substantially decreased the crystallinity of PEO. Two types of inorganic nanofillers were incorporated into these polymer electrolytes. The effects of SiO2 and TiO2 nanofillers on ionic conductivity, crystallinity, and dielectric properties of PEO-EMIHSO 4 were studied over a temperature range from -10 °C and 80 °C. Using an electrochemical capacitor model, impedance (complex capacitance) and dielectric analyses were performed to understand the ionic conduction process with and without fillers in both semi crystalline and amorphous states of the polymer electrolytes. Despite their different nanostructures, both SiO2 and TiO2 promoted an amorphous structure in PEO-EMIHSO 4 and increased the ionic conductivity 2-fold. While in the amorphous state, the 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.

  6. 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

  7. 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.

  8. 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

  9. 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 diffusion contribution, the previously developed first order Stark effect RISD model is reformulated to describe the second order (quadratic) Stark effect-the first order Stark effect vanishes because CO2 does not have a permanent dipole moment. Through this analysis, we characterize the structural fluctuations of CO2 in the ionic liquid solvation environment, which separate into magnitude-only and combined magnitude and directional correlations of the liquid's time dependent electric field. This new methodology will enable highly incisive comparisons between CO2 dynamics in a variety of ionic liquid systems. PMID:26979696

  10. 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 diffusion contribution, the previously developed first order Stark effect RISD model is reformulated to describe the second order (quadratic) Stark effect—the first order Stark effect vanishes because CO2 does not have a permanent dipole moment. Through this analysis, we characterize the structural fluctuations of CO2 in the ionic liquid solvation environment, which separate into magnitude-only and combined magnitude and directional correlations of the liquid's time dependent electric field. This new methodology will enable highly incisive comparisons between CO2 dynamics in a variety of ionic liquid systems.

  11. Photochemical Schiemann Reaction in Ionic Liquids

    PubMed Central

    Heredia-Moya, Jorge; Kirk, Kenneth L.

    2007-01-01

    Photochemical Schiemann reactions of imidazole derivatives 1 and 4 were carried out in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid [bmim][BF4] as solvent. The effects of temperature, co-solvent and wavelength on the rate of the reaction and product yield were examined. The use of ionic liquid increases the yield of the photochemical fluorodediazoniation reaction of 2 at 0°C. Careful temperature control is necessary to minimize the photodecomposition of the ionic liquid in order to increase the yield of product. PMID:18079989

  12. Recent development of ionic liquid stationary phases for liquid chromatography.

    PubMed

    Shi, Xianzhe; Qiao, Lizhen; Xu, Guowang

    2015-11-13

    Based on their particular physicochemical characteristics, ionic liquids have been widely applied in many fields of analytical chemistry. Many types of ionic liquids were immobilized on a support like silica or monolith as stationary phases for liquid chromatography. Moreover, different approaches were developed to bond covalently ionic liquids onto the supporting materials. The obtained ionic liquid stationary phases show multi-mode mechanism including hydrophobic, hydrophilic, hydrogen bond, anion exchange, π-π, and dipole-dipole interactions. Therefore, they could be used in different chromatographic modes including ion-exchange, RPLC, NPLC and HILIC to separate various classes of compounds. This review mainly summarizes the immobilized patterns and types of ionic liquid stationary phases, their retention mechanisms and applications in the recent five years. PMID:26463427

  13. 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.

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. system at room temperature

    NASA Astrophysics Data System (ADS)

    Li, Shaoyuan; Ma, Wenhui; Zhou, Yang; Chen, Xiuhua; Xiao, Yongyin; Ma, Mingyu; Zhu, Wenjie; Wei, Feng

    2014-04-01

    In this paper, the moderately and lightly doped porous silicon nanowires (PSiNWs) were fabricated by the `one-pot procedure' metal-assisted chemical etching (MACE) method in the HF/H2O2/AgNO3 system at room temperature. The effects of H2O2 concentration on the nanostructure of silicon nanowires (SiNWs) were investigated. The experimental results indicate that porous structure can be introduced by the addition of H2O2 and the pore structure could be controlled by adjusting the concentration of H2O2. The H2O2 species replaces Ag+ as the oxidant and the Ag nanoparticles work as catalyst during the etching. And the concentration of H2O2 influences the nucleation and motility of Ag particles, which leads to formation of different porous structure within the nanowires. A mechanism based on the lateral etching which is catalyzed by Ag particles under the motivation by H2O2 reduction is proposed to explain the PSiNWs formation.

  20. 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.

  1. 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 phenomena involved in aluminum deposition on copper in AlCl3-BMIMCl electrolyte was found to be instantaneous followed by diffusion controlled three-dimensional growth of nuclei. Diffusion coefficient (Do) of the electroactive species Al2Cl7¯ ion was in the range from 6.5 to 3.9×10–7 cm2∙s–1 at a temperature of 30°C. Relatively little research efforts have been made toward the fundamental understanding and modeling of the species transport and transformation information involved in ionic liquid mixtures, which eventually could lead to quantification of electrochemical properties. Except that experimental work in this aspect usually is time consuming and expensive, certain characteristics of ionic liquids also made barriers for such analyses. Low vapor pressure and high viscosity make them not suitable for atomic absorption spectroscopic measurement. In addition, aluminum electrodeposition in ionic liquid electrolytes are considered to be governed by multi-component mass, heat and charge transport in laminar and turbulent flows that are often multi-phase due to the gas evolution at the electrodes. The kinetics of the electrochemical reactions is in general complex. Furthermore, the mass transfer boundary layer is about one order of magnitude smaller than the thermal and hydrodynamic boundary layer (Re=10,000). Other phenomena that frequently occur are side reactions and temperature or concentration driven natural convection. As a result of this complexity, quantitative knowledge of the local parameters (current densities, ion concentrations, electrical potential, temperature, etc.) is very difficult to obtain. This situation is a serious obstacle for improving the quality of products, efficiency of manufacturing and energy consumption. The gap between laboratory/batch scale processing with global process control and nanoscale deposit surface and materials specifications needs to be bridged. A breakthrough can only be realized if on each scale the occurring phenomena are understood and quantified. Multiscale numerical modeling nevertheless can help to bridge this gap. In conjunction with various scale experimental efforts, this project was aim to construct the basis for a strategy for innovation, by developing a generally applicable modeling methodology for understanding and controlling the electrochemical processes of aluminum electrodeposition in ionic liquids with the unifying characteristic that they are based on charge-driven mass transfer. The approaches developed in this project will not only be essential for the mass production of aluminum on any pilot scale or industrial level production processes, leading to the development of a new aluminum production technology, but also bring significant benefits to the society in terms of saving energy, reducing pollutants emission and recovering valuable metals.

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

    SciTech Connect

    Dr. Ramana G. Reddy

    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  = 0.40. Nucleation phenomena involved in aluminum deposition on copper in AlCl3-BMIMCl electrolyte was found to be instantaneous followed by diffusion controlled three-dimensional growth of nuclei. Diffusion coefficient (Do) of the electroactive species Al2Cl7¯ ion was in the range from 6.5 to 3.9×10–7 cm2∙s–1 at a temperature of 30°C. Relatively little research efforts have been made toward the fundamental understanding and modeling of the species transport and transformation information involved in ionic liquid mixtures, which eventually could lead to quantification of electrochemical properties. Except that experimental work in this aspect usually is time consuming and expensive, certain characteristics of ionic liquids also made barriers for such analyses. Low vapor pressure and high viscosity make them not suitable for atomic absorption spectroscopic measurement. In addition, aluminum electrodeposition in ionic liquid electrolytes are considered to be governed by multi-component mass, heat and charge transport in laminar and turbulent flows that are often multi-phase due to the gas evolution at the electrodes. The kinetics of the electrochemical reactions is in general complex. Furthermore, the mass transfer boundary layer is about one order of magnitude smaller than the thermal and hydrodynamic boundary layer (ReL≈10,000). Other phenomena that frequently occur are side reactions and temperature or concentration driven natural convection. As a result of this complexity, quantitative knowledge of the local parameters (current densities, ion concentrations, electrical potential, temperature, etc.) is very difficult to obtain. This situation is a serious obstacle for improving the quality of products, efficiency of manufacturing and energy consumption. The gap between laboratory/batch scale processing with global process control and nanoscale deposit surface and materials specifications needs to be bridged. A breakthrough can only be realized if on each scale the occurring phenomena are understood and quantified. Multiscale numerical modeling nevertheless can help to bridge this gap. In conjunction with various scale experimental efforts, this project was aim to construct the basis for a strategy for innovation, by developing a generally applicable modeling methodology for understanding and controlling the electrochemical processes of aluminum electrodeposition in ionic liquids with the unifying characteristic that they are based on charge-driven mass transfer. The approaches developed in this project will not only be essential for the mass production of aluminum on any pilot scale or industrial level production processes, leading to the development of a new aluminum production technology, but also bring significant benefits to the society in terms of saving energy, reducing pollutants emission and recovering valuable metals.

  3. 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.

  4. The Solubility Parameters of Ionic Liquids

    PubMed Central

    Marciniak, Andrzej

    2010-01-01

    The Hildebrand’s solubility parameters have been calculated for 18 ionic liquids from the inverse gas chromatography measurements of the activity coefficients at infinite dilution. Retention data were used for the calculation. The solubility parameters are helpful for the prediction of the solubility in the binary solvent mixtures. From the solubility parameters, the standard enthalpies of vaporization of ionic liquids were estimated. PMID:20559495

  5. 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.

  6. 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

  7. 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).

  8. 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

  9. 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

  10. 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.

  11. Aqueous Solutions of Ionic Liquids: Microscopic Assembly.

    PubMed

    Vicent-Luna, Jose Manuel; Dubbeldam, David; Gómez-Álvarez, Paula; Calero, Sofia

    2016-02-01

    Aqueous solutions of ionic liquids are of special interest, due to the distinctive properties of ionic liquids, in particular, their amphiphilic character. A better understanding of the structure-property relationships of such systems is hence desirable. One of the crucial molecular-level interactions that influences the macroscopic behavior is hydrogen bonding. In this work, we conduct molecular dynamics simulations to investigate the effects of ionic liquids on the hydrogen-bond network of water in dilute aqueous solutions of ionic liquids with various combinations of cations and anions. Calculations are performed for imidazolium-based cations with alkyl chains of different lengths and for a variety of anions, namely, [Br](-) , [NO3 ](-) , [SCN](-) , [BF4 ](-) , [PF6 ](-) , and [Tf2 N](-) . The structure of water and the water-ionic liquid interactions involved in the formation of a heterogeneous network are analyzed by using radial distribution functions and hydrogen-bond statistics. To this end, we employ the geometric criterion of the hydrogen-bond definition and it is shown that the structure of water is sensitive to the amount of ionic liquid and to the anion type. In particular, [SCN](-) and [Tf2 N](-) were found to be the most hydrophilic and hydrophobic anions, respectively. Conversely, the cation chain length did not influence the results. PMID:26641024

  12. The distillation and volatility of ionic liquids

    NASA Astrophysics Data System (ADS)

    Earle, Martyn J.; Esperança, José M. S. S.; Gilea, Manuela A.; Canongia Lopes, José N.; Rebelo, Luís P. N.; Magee, Joseph W.; Seddon, Kenneth R.; Widegren, Jason A.

    2006-02-01

    It is widely believed that a defining characteristic of ionic liquids (or low-temperature molten salts) is that they exert no measurable vapour pressure, and hence cannot be distilled. Here we demonstrate that this is unfounded, and that many ionic liquids can be distilled at low pressure without decomposition. Ionic liquids represent matter solely composed of ions, and so are perceived as non-volatile substances. During the last decade, interest in the field of ionic liquids has burgeoned, producing a wealth of intellectual and technological challenges and opportunities for the production of new chemical and extractive processes, fuel cells and batteries, and new composite materials. Much of this potential is underpinned by their presumed involatility. This characteristic, however, can severely restrict the attainability of high purity levels for ionic liquids (when they contain poorly volatile components) in recycling schemes, as well as excluding their use in gas-phase processes. We anticipate that our demonstration that some selected families of commonly used aprotic ionic liquids can be distilled at 200-300°C and low pressure, with concomitant recovery of significant amounts of pure substance, will permit these currently excluded applications to be realized.

  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. Electrodeposition of nano- and microcrystalline aluminium in three different air and water stable ionic liquids.

    PubMed

    Zein El Abedin, S; Moustafa, E M; Hempelmann, R; Natter, H; Endres, F

    2006-07-17

    The present work shows, for the first time, a comparative experimental study on the electrodeposition of aluminium in three different water and air stable ionic liquids, namely 1-butyl-1-methylpyrrolidinium-bis(trifluoromethylsulfonyl)imide ([BMP]Tf2N), 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide ([EMIm] Tf2N), and trihexyl-tetradecyl-phosphoniumbis(trifluoromethylsulfonyl)imide (P(14,6,6,6) Tf2N). The ionic liquids [BMP]Tf2N and [EMIm]Tf2N show biphasic behaviour in the AlCl3 concentration range from 1.6 to 2.5 mol L(-1) and 2.5 to 5 mol L(-1), respectively. The biphasic mixtures become monophasic at temperatures >/=80 degrees C. It was found that nanocrystalline aluminium can be electrodeposited in the ionic liquid [BMP]Tf2N saturated with AlCl3. The deposits obtained are generally uniform, dense, shining, and adherent with very fine crystallites in the nanometer size regime. However, coarse cubic-shaped aluminium particles in the micrometer range are obtained in the ionic liquid [EMIm]Tf2N. In this liquid the particle size significantly increases as the temperature rises. A very thin, mirrorlike aluminium film containing very fine crystallites of about 20 nm is obtained in the ionic liquid [trihexyl-tetradecyl-phosphonium]Tf(2)N at room temperature. At 150 degrees C, the average grain size is found to be 35 nm. PMID:16789040

  15. Protic ionic liquids: solvents with tunable phase behavior and physicochemical properties.

    PubMed

    Greaves, Tamar L; Weerawardena, Asoka; Fong, Celesta; Krodkiewska, Irena; Drummond, Calum J

    2006-11-16

    The phase behavior, including glass, devitrification, solid crystal melting, and liquid boiling transitions, and physicochemical properties, including density, refractive index, viscosity, conductivity, and air-liquid surface tension, of a series of 25 protic ionic liquids and protic fused salts are presented along with structure-property comparisons. The protic fused salts were mostly liquid at room temperature, and many exhibited a glass transition occurring at low temperatures between -114 and -44 degrees C, and high fragility, with many having low viscosities, down to as low as 17 mPa.s at 25 degrees C, and ionic conductivities up to 43.8 S/cm at 25 degrees C. These protic solvents are easily prepared through the stoichiometric combination of a primary amine and Brønsted acid. They have poor ionic behavior when compared to the far more studied aprotic ionic liquids. However, some of the other physicochemical properties possessed by these solvents are highly promising and it is anticipated that these, or analogous protic solvents, will find applications beyond those already identified for aprotic ionic liquids. This series of protic fused salts was employed to determine the effect of structural changes on the physicochemical properties, including the effect of hydroxyl groups, increasing alkyl chain lengths, branching, and the differences between inorganic and organic anions. It was found that simple structural modifications provide a mechanism to manipulate, over a wide range, the temperature at which phase transitions occur and to specifically tailor physicochemical properties for potential end-use applications. PMID:17091990

  16. Dissolution of wood in ionic liquids.

    PubMed

    Kilpeläinen, Ilkka; Xie, Haibo; King, Alistair; Granstrom, Mari; Heikkinen, Sami; Argyropoulos, Dimitris S

    2007-10-31

    The present paper demonstrates that both hardwoods and softwoods are readily soluble in various imidazolium-based ionic liquids (ILs) under gentle conditions. More specifically, a variety of ionic liquids can only partially dissolve wood chips, whereas ionic liquids such as 1-butyl-3-methylimidazolium chloride and 1-allyl-3-methylimidazolium chloride have good solvating power for Norway spruce sawdust and Norway spruce and Southern pine thermomechanical pulp (TMP) fibers. Despite the fact that the obtained solutions were not fully clear, these ionic liquids provided solutions which permitted the complete acetylation of the wood. Alternatively, transparent amber solutions of wood could be obtained when the dissolution of the same lignocellulosic samples was attempted in 1-benzyl-3-methylimidazolium chloride. This realization was based on a designed augmented interaction of the aromatic character of the cation of the ionic liquid with the lignin in the wood. After dissolution, wood can be regenerated as an amorphous mixture of its original components. The cellulose of the regenerated wood can be efficiently digested to glucose by a cellulase enzymatic hydrolysis treatment. Furthermore, completely acetylated wood was found to be readily soluble in chloroform, allowing, for the first time, detailed proton nuclear magnetic resonance (NMR) spectra and NMR diffusion measurements to be made. It was thus demonstrated that the dissolution of wood in ionic liquids now offers a variety of new possibilities for its structural and macromolecular characterization, without the prior isolation of its individual components. Furthermore, considering the relatively wide solubility and compatibility of ionic liquids with many organic or inorganic functional chemicals or polymers, it is envisaged that this research could create a variety of new strategies for converting abundant woody biomass to valuable biofuels, chemicals, and novel functional composite biomaterials. PMID:17907779

  17. A novel CMPO-functionalized task specific ionic liquid: synthesis, extraction and spectroscopic investigations of actinide and lanthanide complexes.

    PubMed

    Mohapatra, Prasanta K; Kandwal, Pankaj; Iqbal, Mudassir; Huskens, Jurriaan; Murali, Mallekav S; Verboom, Willem

    2013-04-01

    A novel CMPO (carbamoylmethylphosphine oxide) based task specific ionic liquid (TSIL) with an NTf(2)(-) counter anion was synthesized and evaluated for actinide/lanthanide extraction from acidic feed solutions using several room temperature ionic liquids (RTILs). The extraction data were compared with those obtained with CMPO in the same set of RTILs and also in the molecular diluent, n-dodecane. The extracted species were analyzed by the conventional slope analysis method and the extraction followed an ion-exchange mechanism. The nature of bonding in the extracted complexes was investigated by various spectroscopic techniques such as FT-IR and UV-visible spectroscopy. PMID:23403959

  18. 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

  19. 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

  20. 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.

  1. 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

  2. [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

  3. 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.

  4. Solvation thermodynamics of alkali and halide ions in ionic liquids through integral equations.

    PubMed

    Bruzzone, Samantha; Malvaldi, Marco; Chiappe, Cinzia

    2008-08-21

    In this work, we study the solvation thermodynamics and other solvation properties of small ions in two room-temperature ionic liquids, dimethyl imidazolium hexafluorophosphate [mmim] [pf6] and dimethyl imidazolium chloride [mmim][cl] with the reference interaction site model (RISM). The nature of the charge affects several aspects of solvation, from electrostriction to the mutual disposition of cations around the solute; nevertheless, the long-range screening behavior of the liquid appears to be insensitive to both charge and dimensions of the solute. The ion solvation is energy driven, as expected for the nature of the solvent, and displays a marked asymmetry between cation and anion solvation chemical potential. Such asymmetry is dependent, even qualitatively, on the ionic liquid chosen as solvent. Partial molar volumes of ions in solution are found to follow the nature of ion-solvent interaction. PMID:19044785

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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 recover to a bleached state upon exposure to heat and solar radiation while being cycled over time from the bleached to the dark state. Most likely the polymers are undergoing degradation reactions which are accelerated by heat and solar exposure while in either the reduced or oxidized states and the performance of the polymers is greatly reduced over time. For this technology to succeed in an exterior window application, there needs to be more work done to understand the degradation of the polymers under real-life application conditions such as elevated temperatures and solar exposure so that recommendations for improvements in to the overall system can be made. This will be the key to utilizing this type of technology in any future real-life applications.

  10. Ionic liquids as active pharmaceutical ingredients.

    PubMed

    Ferraz, Ricardo; Branco, Luís C; Prudêncio, Cristina; Noronha, João Paulo; Petrovski, Zeljko

    2011-06-01

    Ionic liquids (ILs) are ionic compounds that possess a melting temperature below 100 °C. Their physical and chemical properties are attractive for various applications. Several organic materials that are now classified as ionic liquids were described as far back as the mid-19th century. The search for new and different ILs has led to the progressive development and application of three generations of ILs: 1) The focus of the first generation was mainly on their unique intrinsic physical and chemical properties, such as density, viscosity, conductivity, solubility, and high thermal and chemical stability. 2) The second generation of ILs offered the potential to tune some of these physical and chemical properties, allowing the formation of "task-specific ionic liquids" which can have application as lubricants, energetic materials (in the case of selective separation and extraction processes), and as more environmentally friendly (greener) reaction solvents, among others. 3) The third and most recent generation of ILs involve active pharmaceutical ingredients (API), which are being used to produce ILs with biological activity. Herein we summarize recent developments in the area of third-generation ionic liquids that are being used as APIs, with a particular focus on efforts to overcome current hurdles encountered by APIs. We also offer some innovative solutions in new medical treatment and delivery options. PMID:21557480

  11. 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.

  12. Improved adhesive for cryogenic applications cures at room temperature

    NASA Technical Reports Server (NTRS)

    Klinger, H. J.; Smith, M. B.

    1966-01-01

    Adhesive cured at room temperature provides an effective adhesive bond over the range from room temperature down to the temperature of liquid hydrogen. The adhesive consists of one part of 200-mesh powdered nylon filler to two parts of an epoxy-polyamine resin.

  13. The thiocyanate anion is a primary driver of carbon dioxide capture by ionic liquids

    NASA Astrophysics Data System (ADS)

    Chaban, Vitaly

    2015-01-01

    Carbon dioxide, CO2, capture by room-temperature ionic liquids (RTILs) is a vivid research area featuring both accomplishments and frustrations. This work employs the PM7-MD method to simulate adsorption of CO2 by 1,3-dimethylimidazolium thiocyanate at 300 K. The obtained result evidences that the thiocyanate anion plays a key role in gas capture, whereas the impact of the 1,3-dimethylimidazolium cation is mediocre. Decomposition of the computed wave function on the individual molecular orbitals confirms that CO2-SCN binding extends beyond just expected electrostatic interactions in the ion-molecular system and involves partial sharing of valence orbitals.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. Ionic liquid assisted synthesis of Au-Pd bimetallic particles with enhanced electrocatalytic activity.

    PubMed

    Li, Zhonghao; Li, Rui; Mu, Tiancheng; Luan, Yuxia

    2013-05-01

    Morphology- and composition-controlled synthesis of Au-Pd bimetallic particles was realized by a facile ionic liquid assisted route at room temperature. The morphologies of the synthesized particles, such as nanoflake-constructed spheres with a core-shell structure, nanoparticle-constructed spheres, and nanoparticle-constructed dendrites, could be well controlled by the present route. The ionic liquid was found to play a key role in the formation of these interesting particles. Moreover, the composition (Au:Pd) of the particles could be modulated by means of the molar ratio of the metal precursors in the feeding solutions. The Au-Pd bimetallic particles exhibit high electrocatalytic activity toward oxidation of ethanol and formic acid. Furthermore, cyclic voltammetric studies on the as-prepared Au-Pd bimetallic particles revealed good electroactivity for H2O2, which results in an effective amperometric H2O2 sensor. PMID:23471860

  1. Spectroscopic study on imidazolium-based ionic liquids: effect of alkyl chain length and anion.

    PubMed

    Binetti, Enrico; Panniello, Annamaria; Triggiani, Leonardo; Tommasi, Raffaele; Agostiano, Angela; Curri, Maria Lucia; Striccoli, Marinella

    2012-03-22

    Room temperature ionic liquids are currently used as functional materials in several application and their optical investigation can provide a better understanding of their physical and chemical behavior. Absorption and emission properties of imidazolium-based ILs have been attributed to the imidazolium moiety and related to the presence of energetically different aggregates. Here, time-integrated and time-resolved investigation has been carried out on 1-alkyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate ionic liquids with different chain lengths in order to probe the occurrence of energy transfer processes, and hence to disclose the presence of various states with different energy. Such a study contributes to provide relevant insight on the effect of alkyl chain and anion type on the emission characteristics, and, hence, on the presence of associated structures. PMID:22369210

  2. Electrochemical and physicochemical properties of small phosphonium cation ionic liquid electrolytes with high lithium salt content.

    PubMed

    Girard, G M A; Hilder, M; Zhu, H; Nucciarone, D; Whitbread, K; Zavorine, S; Moser, M; Forsyth, M; MacFarlane, D R; Howlett, P C

    2015-04-14

    Electrolytes of a room temperature ionic liquid (RTIL), trimethyl(isobutyl)phosphonium (P111i4) bis(fluorosulfonyl)imide (FSI) with a wide range of lithium bis(fluorosulfonyl)imide (LiFSI) salt concentrations (up to 3.8 mol kg(-1) of salt in the RTIL) were characterised using a combination of techniques including viscosity, conductivity, differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), nuclear magnetic resonance (NMR) and cyclic voltammetry (CV). We show that the FSI-based electrolyte containing a high salt concentration (e.g. 1 : 1 salt to IL molar ratio, equivalent to 3.2 mol kg(-1) of LiFSI) displays unusual transport behavior with respect to lithium ion mobility and promising electrochemical behavior, despite an increase in viscosity. These electrolytes could compete with the more traditionally studied nitrogen-based ionic liquids (ILs) in lithium battery applications. PMID:25820549

  3. 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)

  4. Polyoxometalate ionic liquids as self-repairing acid-resistant corrosion protection.

    PubMed

    Herrmann, Sven; Kostrzewa, Monika; Wierschem, Andreas; Streb, Carsten

    2014-12-01

    Corrosion is a global problem for any metallic structure or material. Herein we show how metals can easily be protected against acid corrosion using hydrophobic polyoxometalate-based ionic liquids (POM-ILs). Copper metal disks were coated with room-temperature POM-ILs composed of transition-metal functionalized Keggin anions [SiW11 O39 TM(H2 O)](n-) (TM=Cu(II) , Fe(III) ) and quaternary alkylammonium cations (Cn H2 n+1 )4 N(+) (n=7-8). The corrosion resistance against acetic acid vapors and simulated "acid rain" was significantly improved compared with commercial ionic liquids or solid polyoxometalate coatings. Mechanical damage to the POM-IL coating is self-repaired in less than one minute with full retention of the acid protection properties. The coating can easily be removed and recovered by rinsing with organic solvents. PMID:25332068

  5. 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.

  6. Tunable amphiphilicity and multifunctional applications of ionic-liquid-modified carbon quantum dots.

    PubMed

    Wang, Baogang; Song, Aixin; Feng, Lei; Ruan, Hong; Li, Hongguang; Dong, Shuli; Hao, Jingcheng

    2015-04-01

    During the past decade, increasing attention has been paid to photoluminescent nanocarbon materials, namely, carbon quantum dots (CQDs). It is gradually accepted that surface engineering plays a key role in regulating the properties and hence the applications of the CQDs. In this paper, we prepared highly charged CQDs through a one-pot pyrolysis with citric acid as carbon source and a room-temperature imidazolium-based ionic liquid as capping agent. The as-prepared CQDs exhibit high quantum yields up to 25.1% and are stable under various environments. In addition, the amphiphilicity of the CQDs can be facilely tuned by anion exchange, which leads to a spontaneous phase transfer between water and oil phase. The promising applications of the CQDs as ion sensors and fluorescent inks have been demonstrated. In both cases, these ionic-liquid-modified CQDs were found to possess novel characteristics and/or superior functions compared to existing ones. PMID:25774972

  7. 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

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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...

  13. 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...

  14. 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.

  15. Ionic liquid electrolytes for reversible magnesium electrochemistry.

    PubMed

    Kar, Mega; Ma, Zheng; Azofra, Luis Miguel; Chen, Kun; Forsyth, Maria; MacFarlane, Douglas R

    2016-03-01

    Mg has great potential as the basis for a safe, low cost energy storage technology, however, cycling of magnesium is difficult to achieve in most electrolytes. We demonstrate cycling of Mg from a novel alkoxyammonium ionic liquid. DFT calculations highlight the role that Mg coordination with [BH4](-) ions plays in the mechanism. PMID:26888053

  16. 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 Center during this summer is to develop and characterize proton exchange membranes doped with ionic liquids. The main techniques used to characterize these materials are: Impedance Spectroscopy, NMR, DSC, TGA, DMA, IR, and SEM ...

  17. Liquid clathrate formation in ionic liquid-aromatic mixtures.

    PubMed

    Holbrey, John D; Reichert, W Matthew; Nieuwenhuyzen, Mark; Sheppard, Oonagh; Hardacre, Christopher; Rogers, Robin D

    2003-02-21

    1-Alkyl-3-methylimidazolium containing ionic liquids with hexafluorophosphate, bis(trifyl)imide, tetrafluoroborate, and chloride anions form liquid clathrates when mixed with aromatic hydrocarbons; in the system 1,3-dimethylimidazolium hexafluorophosphate-benzene, the aromatic solute could be trapped in the solid state forming a crystalline 2:1 inclusion compound. PMID:12638957

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. Functionalized ionic liquids as electrolytes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Pandian, Shanthi; Raju, S. G.; Hariharan, Krishnan S.; Kolake, Subramanya M.; Park, Da-Hye; Lee, Myung-Jin

    2015-07-01

    The design of potential and new electrochemically stable electrolytes for Li-ion batteries is an important task in the field of energy. Room temperature ionic liquids (RTILs) characterized by a wide electrochemical window (EW) are the commonly used electrolytes for Li battery applications. In this work, a novel quantum computational method is proposed to estimate the electrochemical stability of RTILs that accurately predicts the trends in EWs of ammonium based ILs and is computationally faster than the state-of-the-art methods. Subsequently, the EW of ILs with phosphonium and sulfonium cations are computed and compared against the well-established ammonium congeners. Based on the criterion of electrochemical stability defined with respect to Li, the increasing order of stability is found to be: sulfonium < ammonium < phosphonium based ILs. The effect of various substituents like butyl, phenyl and benzyl on the phosphonium and sulfonium based ILs is examined and a greater stability for the phenyl over other substituents is observed. The key factor influencing the reduction potential of the cations is inferred as the thermodynamic stability of the radical formed during decomposition. Based on the results, design guidelines to identify stable IL systems as electrolytes in high voltage Li-ion battery applications are provided.

  3. Theory of Phase Separation and Polarization for Pure Ionic Liquids.

    PubMed

    Gavish, Nir; Yochelis, Arik

    2016-04-01

    Room temperature ionic liquids are attractive to numerous applications and particularly, to renewable energy devices. As solvent free electrolytes, they demonstrate a paramount connection between the material morphology and Coulombic interactions: the electrode/RTIL interface is believed to be a product of both polarization and spatiotemporal bulk properties. Yet, theoretical studies have dealt almost exclusively with independent models of morphology and electrokinetics. Introduction of a distinct Cahn-Hilliard-Poisson type mean-field framework for pure molten salts (i.e., in the absence of any neutral component), allows a systematic coupling between morphological evolution and the electrokinetic phenomena, such as transient currents. Specifically, linear analysis shows that spatially periodic patterns form via a finite wavenumber instability and numerical simulations demonstrate that while labyrinthine type patterns develop in the bulk, lamellar structures are favored near charged surfaces. The results demonstrate a qualitative phenomenology that is observed empirically and thus, provide a physically consistent methodology to incorporate phase separation properties into an electrochemical framework. PMID:26954098

  4. 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.

  5. 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.

  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. Understanding the large solubility of lidocaine in 1-n-butyl-3-methylimidazolium based ionic liquids using molecular simulation.

    PubMed

    Ley, Ryan T; Paluch, Andrew S

    2016-02-28

    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. PMID:26931706

  8. 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.

  9. 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.

  10. 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 of the [etma][CF{sub 3}SO{sub 3}] ionic liquid.

  11. Ionic liquids as a novel solvent for lanthanide extraction.

    PubMed

    Nakashima, Kazunori; Kubota, Fukiko; Maruyama, Tatsuo; Goto, Masahiro

    2003-08-01

    Octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) dissolved in an ionic liquids, 1-butyl-3-methyl-imidazolium hexafluorophosphate, greatly enhances extractability and selectivity of lanthanide cations compared to that dissolved in conventional organic solvents; further, the recovery of lanthanides extracted into ionic liquids can be accomplished using several stripping solutions containing complexing agents. The possibility of utilizing ionic liquids as novel separation media in an industrial liquid-liquid extraction process was demonstrated. PMID:12945658

  12. 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

  13. Understanding the Solubility of Acetaminophen in 1-n-Alkyl-3-methylimidazolium-Based Ionic Liquids Using Molecular Simulation.

    PubMed

    Paluch, Andrew S; Lourenço, Tuanan C; Han, Fenglin; Costa, Luciano T

    2016-04-01

    During the manufacturing of pharmaceutical compounds, solvent mixtures are commonly used, where the addition of a cosolvent allows for the tuning of the intermolecular interactions present in the system. Here we demonstrate how a similar effect can be accomplished using a room temperature ionic liquid. The pharmaceutical compound acetaminophen is studied in 21 common ionic liquids composed of a 1-n-alkyl-3-methylimidazolium cation with 1 of 7 anions. Using the acetate anion, we predict a large enhancement in solubility of acetaminophen relative to water. We show how this is caused by a synergistic effect of favorable interactions between the ionic liquid and the phenyl, hydroxyl and amide groups of acetaminophen, demonstrating how the ionic liquid cation and anion may be chosen to preferentially solvate different functional groups of complex pharmaceutical compounds. Additionally, while the use of charge scaling in ionic liquid force fields has previously been found to have a minute effect on ionic liquid structural properties, we find it appreciably affects the computed solvation free energy of acetaminophen, which in turn affects the predicted solubility. PMID:26974037

  14. 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.

  15. Employment of ionic liquid-imbibed polymer gel electrolyte for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Li, Qinghua; Tang, Qunwei; Du, Nan; Qin, Yuancheng; Xiao, Jin; He, Benlin; Chen, Haiyan; Chu, Lei

    2014-02-01

    Volatility of organic solvent in liquid electrolyte has been tremendous obstacle for its application in dye-sensitized solar cells (DSSCs), here we designed an ionic liquid-imbibed polymer gel electrolyte using 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as solvent, 1-methyl-3-propylimidazolium iodide (MPII) as iodine source, and amphiphilic poly(hydroxyethyl methacrylate/glycerol) [poly(HEMA/GR)] as a placeholder. As an amphiphilic matrix, poly(HEMA/GR) material can swell in ionic liquid electrolyte to form a stable gel, benefiting from its extraordinary absorption. The imbibed ionic liquid electrolyte is stored into interconnected poly(HEMA/GR) framework. Resultant quasi-solid-state electrolyte is honored with high ionic conductivity (14.29 mS cm-1) at room temperature and good retention. The ionic liquid-imbibed poly(HEMA/GR) gel electrolyte-based DSSC gives an overall light-to-electric conversion efficiency of 7.15%. The new concept along with easy fabrication promises the ionic liquid-imbibed gel electrolytes good alternatives in efficient DSSCs.

  16. 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

  17. 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

  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. 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

  20. 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.

  1. 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.

  2. 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.

  3. Electrochemical biosensing platform based on amino acid ionic liquid functionalized graphene for ultrasensitive biosensing applications.

    PubMed

    Lu, Xianbo; Wang, Xue; Jin, Jing; Zhang, Qing; Chen, Jiping

    2014-12-15

    In this study, a facile non-covalent method was developed for preparing water-soluble graphene with excellent electronic conductivity. Room temperature ionic liquids (ILs) with high ionic conductivity were used for the non-covalent surface functionalization of graphene through π-π stacking interactions. Compared to other ILs used, amino acid ionic liquids (AAILs) were found to be the most effective for improving the dispersion of graphene in water phase. Electrochemical and spectroscopic results confirmed that the obtained AAIL functionalized GR can retain the excellent electronic conductivity of pristine graphene without damaging the graphene lattice. The obtained water-soluble graphene (GR-AAIL) was exemplified to fabricate an electrochemical biosensor using tyrosinase as a model enzyme, and the sensitivity (12,600 mA cm(-2) M(-1)) of GR-AAIL based biosensor was about 17 times higher than that of graphene oxide and other nanomaterial based biosensor, displaying its unprecedented high sensitivity for biosensing. The detection limit for catechol (one important environmental pollutant) reached as low as 8 nM with a response time of 3s and a linear range from 25 nM to 11,100 nM. The AAIL-GR based biosensor also demonstrated good reproducibility, repeatability, selectivity, long-term stability and high recovery for catechol detection. Amino acid ionic liquid functionalized graphene proves to be a robust and versatile electrochemical biosensing platform for fabricating biosensors with excellent performance. PMID:24997366

  4. 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.

  5. 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

  6. 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

  7. Mirrorless dye doped ionic liquid lasers.

    PubMed

    Barna, Valentin; De Cola, Luisa

    2015-05-01

    The study of electromagnetic waves propagation in periodically structured dielectrics and the linear and nonlinear optical phenomena in disordered systems doped with gain media represent one of the most challenging and exciting scientific areas of the past decade. Lasing and Random Lasers (RL) are fascinating examples of topics that synergize multiple scattering of light and optical amplification and lately have been the subject of intense theoretical and experimental studies. In this manuscript we demonstrate laser action in a new category of materials, namely dye doped ionic liquids. Ionic liquids prove to be perfect candidates for building, as shown, a series of exotic boundaryless or confined compact laser systems. Lasing is presented in standard wedge cells, freely suspended ionic liquid films and droplets. The optical emission properties are investigated in terms of spectral analysis, below and above lasing energy threshold behavior, emission efficiency, far field spatial laser modes intensity profiling, temporal emission behavior etc. As demonstrated, these materials can be employed as optimal near future replacements of conventional flammable solvents in already available dye laser instruments. PMID:25969283

  8. 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

  9. 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

  10. Simulations of ionic liquids, solutions, and surfaces.

    PubMed

    Lynden-Bell, Ruth M; Del Pópolo, Mario G; Youngs, Tristan G A; Kohanoff, Jorge; Hanke, Christof G; Harper, Jason B; Pinilla, Carlos C

    2007-11-01

    We have been using atomistic simulation for the last 10 years to study properties of imidazolium-based ionic liquids. Studies of dissolved molecules show the importance of electrostatic interactions in both aromatic and hydrogen-bonding solutes. However, the local structure strongly depends upon ion-ion and solute-solvent interactions. We find interesting local alignments of cations at the gas-liquid and solid-liquid interfaces, which give a potential drop through the surface. If the solid interface is charged, this charge is strongly screened over distances of a few nanometres and this screening decays on a fast time scale. We have studied the sensitivity of the liquid structure to force-field parameters and show that results from ab initio simulations can be used in the development of force fields. PMID:17914887

  11. 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

  12. 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.

  13. How polar are ionic liquids? Determination of the static dielectric constant of an imidazolium-based ionic liquid by microwave dielectric spectroscopy.

    PubMed

    Wakai, Chihiro; Oleinikova, Alla; Ott, Magnus; Weingärtner, Hermann

    2005-09-15

    In a pilot study of the dielectric constant of room-temperature ionic liquids, we use dielectric spectroscopy in the megahertz/gigahertz regime to determine the complex dielectric function of five 1-alkyl-3-methylimidazolium salts, from which the static dielectric constant epsilon is obtained by zero-frequency extrapolation. The results classify the salts as moderately polar solvents. The observed epsilon-values at 298.15 K fall between 15.2 and 8.8, and epsilon decreases with increasing chain length of the alkyl residue of the cation. The anion sequence is trifluoromethylsulfonate > tetrafluoroborate approximately tetrafluorophosphate. The results indicate markedly lower polarities than found by spectroscopy with polarity-sensitive solvatochromic dyes. PMID:16853170

  14. 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

  15. 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

  16. Aggregation behavior of long-chain ionic liquids in an ionic liquid.

    PubMed

    Li, Na; Zhang, Shaohua; Zheng, Liqiang; Dong, Bin; Li, Xinwei; Yu, Li

    2008-08-14

    The aggregation behavior of long-chain ionic liquids 1-alkyl-3-methylimidazolium bromide (C(n)mimBr) in another ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), was studied for the first time. Surface tension measurements revealed that aggregates are formed by C(n)mimBr, and freeze fracture transmission electron microscopy (FF-TEM) observations suggested the aggregates are spheres with a size much larger than traditional micelles. The sizes of the aggregates were further confirmed by dynamic light scattering (DLS) measurements. PMID:18654675

  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. 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

  19. 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

  20. 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 for Zn a 2+ state in the ZnO lattice. Ferromagnetic Resonance (FMR) technique is used to confirm the existence of ferromagnetic ordering at temperatures as high as 425K. The ab initio calculations were found to be consistent with the observation of ferromagnetism arising from fully polarized Mn 2+ state. The key to observed room temperature ferromagnetism in this system is the low temperature processing, which prevents formation of clusters, secondary phases and the host ZnO from becoming n-type. The electronic structure of the same Mn doped ZnO thin films studied using XAS, XES and RIXS, revealed a strong hybridization between Mn 3d and O 2p states, which is an important characteristic of a Dilute magnetic Semiconductor (DMS). It is shown that the various processing conditions like sintering temperature, dopant concentration and the properties of precursors used for making of DMS have a great influence on the final properties. Use of various experimental techniques to verify the physical properties, and to understand the mechanism involved to give rise to ferromagnetism is presented. Methods to improve the magnetic moment in Mn doped ZnO are also described. New promising DMS materials (such as Cu doped ZnO are explored). The demonstrated new capability to fabricate powder, pellets, and thin films of room temperature ferromagnetic semiconductors thus makes possible the realization of a wide range of complex elements for a variety of new multifunctional phenomena related to Spintronic devices as well as magneto-optic components.

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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 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. Electronic supplementary information (ESI) available: Ion diameter distribution (grain size analysis) for the PAN + metal ion solutions. See DOI: 10.1039/c5nr05833c

  6. Development of an Analytical Method Based on Temperature Controlled Solid-Liquid Extraction Using an Ionic Liquid as Solid Solvent.

    PubMed

    Pan, Zhongwei; Wang, Zhengquan; Zhu, Linna; Zhu, Zhiming; Cai, Jinying; Shen, Xiaoman; Fan, Tingli; Zhang, Yingnan; Chen, Zhixiu

    2015-01-01

    At the present paper, an analytical method based on temperature controlled solid-liquid extraction (TC-SLE) utilizing a synthesized ionic liquid, (N-butylpyridinium hexafluorophosphate, [BPy]PF₆), as solid solvent and phenanthroline (PT) as an extractant was developed to determine micro levels of Fe(2+) in tea by PT spectrophotometry. TC-SLE was carried out in two continuous steps: Fe(2+) can be completely extracted by PT-[BPy]PF₆ or back-extracted at 80 °C and the two phases were separated automatically by cooling to room temperature. Fe(2+), after back-extraction, needs 2 mol/L HNO₃ as stripping agent and the whole process was determined by PT spectrophotometry at room temperature. The extracted species was neutral Fe(PT)mCl₂ (m = 1) according to slope analysis in the Fe(2+)-[BPy]PF₆-PT TC-SLE system. The calibration curve was Y = 0.20856X - 0.000775 (correlation coefficient = 0.99991). The linear calibration range was 0.10-4.50 μg/mL and the limit of detection for Fe(2+) is 7.0 × 10(-2) μg/mL. In this method, the contents of Fe(2+) in Tieguanyin tea were determined with RSDs (n = 5) 3.05% and recoveries in range of 90.6%-108.6%. PMID:26690398

  7. 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.

  8. 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 Natlia D S

    2016-01-20

    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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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 cationanion pairing interactions. Furthermore, facile and controlled emission color mixing is demonstrated through combining different ILs, with emission colors ranging from blue to yellow.

  15. 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.

  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

    SciTech Connect

    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. Ion gels prepared by in situ radical polymerization of vinyl monomers in an ionic liquid and their characterization as polymer electrolytes.

    PubMed

    Susan, Md Abu Bin Hasan; Kaneko, Taketo; Noda, Akihiro; Watanabe, Masayoshi

    2005-04-01

    To realize polymer electrolytes with high ionic conductivity, we exploited the high ionic conductivity of an ionic liquid. In situ free radical polymerization of compatible vinyl monomers in a room temperature ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI), afforded a novel series of polymer electrolytes. Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films. The glass transition temperatures of the gels, which we named "ion gels", decreased with increasing mole fraction of EMITFSI and behaved as a completely compatible binary system of poly(methyl methacrylate) (PMMA) and EMITFSI. The temperature dependence of the ionic conductivity of the ion gels followed the Vogel-Tamman-Fulcher (VTF) equation, and the ionic conductivity at ambient temperature reached a value close to 10(-2) S cm(-1). Similarly to the behavior of the ionic liquid, the cation in the ion gels diffused faster than the anion. The number of carrier ions, calculated from the Nernst-Einstein equation, was found to increase for an ion gel from the corresponding value for the ionic liquid itself. The cation transference number increased with decreasing EMITFSI concentration due to interaction between the PMMA matrix and the TFSI(-) anion, which prohibited the formation of ion clusters or associates, as was the case for the ionic liquid itself. PMID:15796564

  19. 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.

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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…

  6. 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

  7. Exploring spectroscopic and physicochemical properties of new fluorescent ionic liquids.

    PubMed

    Marwani, Hadi M

    2013-03-01

    In the current study, spectroscopic and physicochemical properties of newly prepared ionic liquids were investigated. Ionic liquids were synthesized via a simple and straightforward route using a metathesis reaction of either N,N-diethyl-p-phenylenediamine monohydrochloride or N-phenacylpyridinium bromide with bis(trifluoromethane)sulfonimide lithium in water. High yield and purity were obtained for the resultant ionic liquids. Data acquired by use of (1)H NMR and FT-IR measurements were consistent with the chemical structures of newly prepared ionic liquids. Results of thermal gravimetric analysis also implied that these ionic liquids have good thermal stability. In addition, UV-vis and fluorescence spectroscopy measurements provided that new ionic liquids are good absorbent and fluorescent. Time-based fluorescence steady-state measurements showed that ionic liquids have high photostability against photobleaching. For a deeper mechanistic understanding of the analytical potential of newly synthesized ionic liquids, spectroscopic and physicochemical parameters, including singlet absorption, extinction coefficient, fluorescence quantum yield, Stokes shift, oscillator strength and dipole moment, were also investigated. PMID:23117624

  8. 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.

  9. 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

  10. 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.

  11. Nanoparticle Capping Agent Controlled Electron-Transfer Dynamics in Ionic Liquids.

    PubMed

    Tanner, Eden E L; Batchelor-McAuley, Christopher; Compton, Richard G

    2016-04-18

    Herein, we report a change in the mechanism of the oxidation of silver nanoparticles (Ag NPs) with the molecular weight of a poly(ethylene) glycol (PEG) capping agent. Characterisation of the modified nanoparticles is undertaken using dynamic light scattering and UV/Vis spectroscopy. Electrochemical analyses reveal that the oxidation of 6000 molecular weight (MW) PEG is consistent with a polymer-gated mechanism, whilst for 2000 MW PEG the polymer does not hinder the oxidation. The 10,000 MW PEG Ag NPs are rendered almost electrochemically inactive. This study demonstrates the ability to alter and better understand the electron-transfer mechanism in a room temperature ionic liquid (RTIL) by systematically altering the capping agent. PMID:26997502

  12. 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

  13. Non-aqueous aluminium-air battery based on ionic liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Revel, Renaud; Audichon, Thomas; Gonzalez, Serge

    2014-12-01

    A promising metal-air secondary battery based on aluminium-oxygen couple is described. In this paper, we observed that an aluminium-air battery employing EMImCl, AlCl3 room temperature ionic liquid (RTIL) as electrolyte and aluminium as negative electrode, has an exceptional reduced self-discharged rate. Due to its new and innovative type of electrolyte, this aluminium-air battery can support relatively high current densities (up to 0.6 mA cm-2) and an average voltage of 0.6-0.8 V. Such batteries may find immediate applications, as they can provide an internal, built-in autonomous and self-sustained energy source.

  14. Memory effect in an ionic liquid matrix containing single-walled carbon nanotubes and polystyrene

    NASA Astrophysics Data System (ADS)

    Wei, Di; Baral, Jayanta K.; Österbacka, Ronald; Ivaska, Ari

    2008-02-01

    We report the use of an ionic liquid (IL) gel matrix containing a blend of single-walled carbon nanotubes (SWNTs) and polystyrene (PS) as a memory device. SWNTs and PS beads were mixed in a room-temperature IL, 1-butyl-3-methyl-hexafluorophosphate ([BMIM][PF6]). The composite gel was sandwiched between a bottom ITO glass and a top aluminium electrode. By merely changing the concentrations of SWNTs in the inert insulating PS matrix, we observed several distinct electrical properties of the device, such as an insulator, a memory in terms of switching and negative differential resistance (NDR), and a conductor. The electric bistable switching hops between a higher impedance (OFF) state and a lower impedance (ON) state which is approximately equal to five orders of current decays.

  15. Binding Selectivity of Macrocycle Ionophores in Ionic Liquids versus Aqueous Solution and Solvent-free Conditions.

    PubMed

    Gámez, Francisco; Hortal, Ana R; Hurtado, Paola; Avilés-Moreno, Juan R; Hamad, Said; Martínez-Haya, Bruno

    2015-12-01

    The understanding of supramolecular recognition in room-temperature ionic liquids (RTILs) is key to develop the full potential of these materials. In this work, we provide insights into the selectivity of the binding of alkali metal cations by standard cyclodextrin and calixarene macrocycles in RTILs. A direct laser desorption/ionization mass spectrometry approach is employed to determine the relative abundances of the inclusion complexes formed through competitive binding in RTIL solutions. The results are compared with the binding selectivities measured under solvent-free conditions and in water/methanol solutions. Cyclodextrins and calixarenes in which the peripheral OH groups are substituted by bulkier side groups preferentially bind to Cs(+) . Such specific ionophoric behavior is substantially enhanced by solvation effects in the RTIL. This finding is rationalized with the aid of quantum mechanical calculations, in terms of the conformational features and steric interactions that drive the solvation of the inclusion complexes by the bulky RTIL counterions. PMID:26346407

  16. Thermoreversible gelation of an ionic liquid by crystallization of a dissolved polymer.

    PubMed

    Harner, John M; Hoagland, David A

    2010-03-18

    Poly(ethylene glycol) (PEG) dissolves in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO(4)] above approximately 60 degrees C, the neat polymer's melting temperature, and if polymer concentration and molecular weight are high enough, the solution transforms into a semitransparent gel when cooled. The modulus, reaching 100 KPa or higher, is strongly affected by PEG concentration, and self-supporting materials are made even from solutions somewhat below coil overlap. Via differential scanning calorimetry (DSC), rheology, and optical microscopy, thermoreversible solidification is traced to kinetically frustrated polymer crystallization, an established mechanism for many pairings of crystallizable polymer with aqueous or organic solvent. Optical microscopy reveals nucleation and growth of PEG crystals with a largest dimension of tens to hundreds of micrometers. Crystalline chain packing in gels is identical to that of neat PEG, and degrees of crystallization are similar. Simple preparation, nontoxicity, and vanishing volatility suggest unique new gel applications. PMID:20175543

  17. Metsulfuron-methyl-based herbicidal ionic liquids.

    PubMed

    Pernak, Juliusz; Niemczak, Micha?; Shamshina, Julia L; Gurau, Gabriela; G?owacki, Grzegorz; Praczyk, Tadeusz; Marcinkowska, Katarzyna; Rogers, Robin D

    2015-04-01

    Ten sulfonylurea-based herbicidal ionic liquids (HILs) were prepared by combining the metsulfuron-methyl anion with various cation types including quaternary ammonium ([bis(2-hydroxyethyl)methyloleylammonium](+), [2-hydroxyethyltrimethylammonium](+)), pyridinium ([1-dodecylpyridinium](+)), piperidinium ([1-methyl-1-propylpiperidinium](+)), imidazolium ([1-allyl-3-methylimidazolium](+), [1-butyl-3-methylimidazolium](+)), pyrrolidinium ([1-butyl-1-methylpyrrolidinium](+)), morpholinium ([4-decyl-4-methylmorpholinium](+)), and phosphonium ([trihexyltetradecylphosphonium](+) and [tetrabutylphosphonium](+)). Their herbicidal efficacy was studied in both greenhouse tests and field trials. Preliminary results for the greenhouse tests showed at least twice the activity for all HILs when compared to the activity of commercial Galmet 20 SG, with HILs with phosphonium cations being the most effective. The results of two-year field studies showed significantly less enhancement of activity than observed in the greenhouse; nonetheless, it was found that the herbicidal efficacy was higher than that of the commercial analog, and efficacy varied depending on the plant species. PMID:25734891

  18. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

    2006-10-10

    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.

  19. Oxidoreductase behavior in ionic liquids: a review.

    PubMed

    Pinto, Paula C A G; Saraiva, M Lúcia M F S; Lima, José L F C

    2008-10-01

    Due to their unique characteristics ionic liquids (ILs) have been extensively used as solvents in enzymatic procedures, proving to be advantageous alternatives to conventional organic solvents. The studies of enzyme behavior in ILs have increased exponentially in the last years and oxidoreductases particularly have recently started to be studied. The association of oxidoreductases with IL is very promising due to the large field of application of these enzymes. The materials are very interesting not only from the analytical point of view but also in the biocatalytic perspective. In this review, we discuss the behavior of oxidoreductases in the presence of ILs, the mechanisms involved in this association and the immobilization of oxidoreductases in composite materials with IL. The performance of proteins with peroxidase activity in ILs is also reviewed. Future trends and perspectives related with the development of biocatalytic studies involving oxidoreductases and ILs are also considered. PMID:18845879

  20. 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).

  1. Synthesis of Crystalline Chalcogenides in Ionic Liquids.

    PubMed

    Santner, Silke; Heine, Johanna; Dehnen, Stefanie

    2016-01-18

    Crystalline chalcogenides belong to the most promising class of materials. In addition to dense solid-state structures, they may form molecular cluster arrangements and networks with high porosity, as in the so-called "zeotype" chalcogenidometalates. The high structural diversity comes along with interesting physical properties such as semi-/photoconductivity, ion transport capability, molecular trapping potential, as well as chemical and catalytic activity. The great interest in the development of new and tailored chalcogenides has provoked a continuous search for new and better synthesis strategies over the years. The trend has clearly been towards lower temperatures for both economic and ecological reasons as well as for better reaction control. This led to the application of ionic liquids as a designer-like medium for materials synthesis. In this Review, we summarize recent developments and present a survey of different chalcogenide families along with their properties. PMID:26661858

  2. Microwave-assisted synthesis using ionic liquids.

    PubMed

    Martínez-Palou, Rafael

    2010-02-01

    The research and application of green chemistry principles have led to the development of cleaner processes. In this sense, during the present century an ever-growing number of studies have been published describing the use of ionic liquids (ILs) as solvents, catalysts, or templates to develop more environmentally friendly and efficient chemical transformations for their use in both academia and industry. The conjugation of ILs and microwave irradiation as a non-conventional heating source has shown evident advantages when compared to conventional synthetic procedures for the generation of fast, efficient, and environmental friendly synthetic methodologies. This review focuses on the advances in the use of ILs in organic, polymers and materials syntheses under MW irradiation conditions. PMID:19507045

  3. 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.

  4. 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.

  5. Carbon Dioxide and Ionic Liquid Refrigerants: Compact, Efficient Air Conditioning with Ionic Liquid-Based Refrigerants

    SciTech Connect

    2010-10-01

    BEETIT Project: Notre Dame is developing an air-conditioning system with a new ionic liquid and CO2 as the working fluid. Synthetic refrigerants used in air conditioning and refrigeration systems are potent GHGs and can trap 1,000 times more heat in the atmosphere than CO2 alone—making CO2 an attractive alternative for synthetic refrigerants in cooling systems. However, operating cooling systems with pure CO2 requires prohibitively high pressures and expensive hardware. Notre Dame is creating a new fluid made of CO2 and ionic liquid that enables the use of CO2 at low pressures and requires minimal changes to existing hardware and production lines. This new fluid also produces no harmful emissions and can improve the efficiency of air conditioning systems— enabling new use of CO2 as a refrigerant in cooling systems.

  6. 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 < ? < 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 ) 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.

  7. Layering of ionic liquids on rough surfaces

    NASA Astrophysics Data System (ADS)

    Sheehan, Alexis; Jurado, L. Andres; Ramakrishna, Shivaprakash N.; Arcifa, Andrea; Rossi, Antonella; Spencer, Nicholas D.; Espinosa-Marzal, Rosa M.

    2016-02-01

    Understanding the behavior of ionic liquids (ILs) either confined between rough surfaces or in rough nanoscale pores is of great relevance to extend studies performed on ideally flat surfaces to real applications. In this work we have performed an extensive investigation of the structural forces between two surfaces with well-defined roughness (<9 nm RMS) in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by atomic force microscopy. Statistical studies of the measured layer thicknesses, layering force, and layering frequency reveal the ordered structure of the rough IL-solid interface. Our work shows that the equilibrium structure of the interfacial IL strongly depends on the topography of the contact.Understanding the behavior of ionic liquids (ILs) either confined between rough surfaces or in rough nanoscale pores is of great relevance to extend studies performed on ideally flat surfaces to real applications. In this work we have performed an extensive investigation of the structural forces between two surfaces with well-defined roughness (<9 nm RMS) in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by atomic force microscopy. Statistical studies of the measured layer thicknesses, layering force, and layering frequency reveal the ordered structure of the rough IL-solid interface. Our work shows that the equilibrium structure of the interfacial IL strongly depends on the topography of the contact. Electronic supplementary information (ESI) available: Optimized geometries and sizes for [HMIM] Ntf2, SEM images of the smooth and rough colloids, frequency of occurrence of layering in the resolved force-distance curves for all investigated systems with [HMIM] Ntf2, layer size and layering force measured with a sharp tip on mica for the same IL, and results of the kinetics experiments. See DOI: 10.1039/c5nr07805a

  8. Physics of transduction in ionic liquid-swollen Nafion membranes

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew; Leo, Donald

    2006-03-01

    Ionic polymer transducers are a class of electroactive polymers that are able to generate large strains (1-5%) in response to low voltage inputs (1-5 V). Additionally, these materials generate electrical charge in response to mechanical strain and are therefore able to operate as soft, distributed sensors. Traditionally, ionic polymer transducers have been limited in their application by their hydration dependence. This work seeks to overcome this limitation by replacing the water with an ionic liquid. Ionic liquids are molten salts that exhibit very high thermal and electrochemical stability while also possessing high ionic conductivity. Results have shown that an ionic liquid-swollen ionic polymer transducer can operate for more than 250,000 cycles in air as compared to about 2,000 cycles for a water-swollen transducer. The current work examines the mechanisms of transduction in ionic liquid-swollen transducers based on Nafion polymer membranes. Specifically, the morphology and relevant ion associations within these membranes are investigated by the use of small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). These results reveal that the ionic liquid interacts with the membrane in much the same way that water does, and that the counterions of the Nafion polymer are the primary charge carriers. The results of these analyses are compared to the macroscopic transduction behavior in order to develop a model of the charge transport mechanism responsible for electromechanical coupling in these membranes.

  9. Direct write dispenser printing of a zinc microbattery with an ionic liquid gel electrolyte

    NASA Astrophysics Data System (ADS)

    Ho, C. C.; Evans, J. W.; Wright, P. K.

    2010-10-01

    The need for energy dense microbatteries with miniature dimensions has prompted the development of unconventional materials, cell geometries, and processing methods. This work will highlight our materials investigations, deposition methods and the device performance of a printed zinc-manganese dioxide rechargeable microbattery utilizing an ionic liquid gel electrolyte. We have developed a direct write dispenser printing method with the ability to fabricate multilayer structures and precisely deposit and pattern these components onto any substrates. The use of a unique room-temperature ionic liquid swelled into a polymer to form a gel electrolyte with solid-like mechanical strength and liquid-like ion transport properties has enabled the simple fabrication of stacked microbattery structures with the potential to be easily integrated directly onto a microdevice substrate. Initial microbattery tests and cycle behavior are discussed, and after an initial activation of the cathode material, an experimental cell discharge capacity and energy density of 0.98 mA h cm-2 and 1.2 mW h cm-2 were measured, respectively.

  10. Preparation of magnetic ionic liquid/chitosan/graphene oxide composite and application for water treatment.

    PubMed

    Li, Leilei; Luo, Chuannan; Li, Xiangjun; Duan, Huimin; Wang, Xiaojiao

    2014-05-01

    Magnetic chitosan and graphene oxide-ionic liquid (MCGO-IL) composites as biodegradable biosorbents were synthesized by impregnating MCGO with ionic liquid. The characteristic results of FTIR, SEM, and XRD showed that MCGO-IL were successfully prepared with large surface area and good magnetic responsiveness. They were used for the removal of Cr(VI) from simulated wastewater with a fast solid-liquid separation in the presence of external magnetic field. The influence of various analytical parameters on the adsorption of Cr(VI) such as pH, contact time, and initial ion concentration were studied in detail. The adsorption followed a pseudo-second-order kinetics. The equilibrium adsorption was well-described by the Langmuir isotherm mode and the maximum adsorption capacity was 145.35 mg/g. The stronger intermolecular hydrogen bond between MCGO-IL and Cr(VI) and the hydroxyl and amine groups were believed to be the metal ion binding sites. Moreover, the MCGO-IL could be repeatedly used by simple treatment without obvious structure and performance degradation. The obtained results indicated that the impregnation of the room temperature IL significantly enhances the removal efficiency of Cr(VI). The MCGO-IL may be suitable materials in heavy metal ion pollution cleanup if they are synthesized in large scale and at low price in near future. PMID:24560948

  11. Reaction of pharmacological active tris-(2-hydroxyethyl)ammonium 4-chlorophenylsulfanylacetate with ZnCl2 or NiCl2: first conversion of a protic ionic liquid into metallated ionic liquid

    PubMed Central

    2013-01-01

    The reaction of pharmacological active protic ionic liquid tris-(2-hydroxyethyl)ammonium 4-chlorophenylsulfanylacetate H+N(CH2CH2OH)3 ∙ (-OOCCH2SC6H4Cl-4) (1) with zinc or nickel chloride in a ratio of 2:1 affords stable at room temperature powder-like adducts [H+N(CH2CH2OH)3]2 ∙ [M(OOCCH2SC6H4Cl-4)2Cl2]2-, M = Zn (2), Ni (3). By recrystallization from aqueous alcohol compound 2 unexpectedly gives Zn(OOCCH2SC6H4Cl-4)2 ∙ 2H2O (4). Unlike 2, compound 3 gives crystals [N(CH2CH2OH)3]2Ni2+ · [-OOCCH2SC6H4Cl-4]2 (5), which have a structure of metallated ionic liquid. The structure of 5 has been proved by X-ray diffraction analysis. It is the first example of the conversion of a protic ionic liquid into potentially biological active metallated ionic liquid (1 → 3 → 5). PMID:23421876

  12. Electrodrift purification of materials for room temperature radiation detectors

    DOEpatents

    James, R.B.; Van Scyoc, J.M. III; Schlesinger, T.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 is disclosed. 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. 4 figs.

  13. 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.

  14. Topological Insulators at Room Temperature

    SciTech Connect

    Zhang, Haijun; Liu, Chao-Xing; Qi, Xiao-Liang; Dai, Xi; Fang, Zhong; Zhang, Shou-Cheng; /Stanford U., Phys. Dept.

    2010-03-25

    Topological insulators are new states of quantum matter with surface states protected by the time-reversal symmetry. In this work, we perform first-principle electronic structure calculations for Sb{sub 2}Te{sub 3}, Sb{sub 2}Se{sub 3}, Bi{sub 2}Te{sub 3} and Bi{sub 2}Se{sub 3} crystals. Our calculations predict that Sb{sub 2}Te{sub 3}, Bi{sub 2}T e{sub 3} and Bi{sub 2}Se{sub 3} are topological insulators, while Sb{sub 2}Se{sub 3} is not. In particular, Bi{sub 2}Se{sub 3} has a topologically non-trivial energy gap of 0.3eV , suitable for room temperature applications. We present a simple and unified continuum model which captures the salient topological features of this class of materials. These topological insulators have robust surface states consisting of a single Dirac cone at the {Lambda} point.

  15. Direct extraction of genomic DNA from maize with aqueous ionic liquid buffer systems for applications in genetically modified organisms analysis.

    PubMed

    Gonzalez García, Eric; Ressmann, Anna K; Gaertner, Peter; Zirbs, Ronald; Mach, Robert L; Krska, Rudolf; Bica, Katharina; Brunner, Kurt

    2014-12-01

    To date, the extraction of genomic DNA is considered a bottleneck in the process of genetically modified organisms (GMOs) detection. Conventional DNA isolation methods are associated with long extraction times and multiple pipetting and centrifugation steps, which makes the entire procedure not only tedious and complicated but also prone to sample cross-contamination. In recent times, ionic liquids have emerged as innovative solvents for biomass processing, due to their outstanding properties for dissolution of biomass and biopolymers. In this study, a novel, easily applicable, and time-efficient method for the direct extraction of genomic DNA from biomass based on aqueous-ionic liquid solutions was developed. The straightforward protocol relies on extraction of maize in a 10 % solution of ionic liquids in aqueous phosphate buffer for 5 min at room temperature, followed by a denaturation step at 95 °C for 10 min and a simple filtration to remove residual biopolymers. A set of 22 ionic liquids was tested in a buffer system and 1-ethyl-3-methylimidazolium dimethylphosphate, as well as the environmentally benign choline formate, were identified as ideal candidates. With this strategy, the quality of the genomic DNA extracted was significantly improved and the extraction protocol was notably simplified compared with a well-established method. PMID:25381609

  16. Nanostructural organization and anion effects on the temperature dependence of the optical Kerr effect spectra of ionic liquids.

    PubMed

    Xiao, Dong; Rajian, Justin Rajesh; Cady, Amanda; Li, Shengfu; Bartsch, Richard A; Quitevis, Edward L

    2007-05-10

    The intermolecular spectra of three imidazolium ionic liquids were studied as a function of temperature by the use of optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids comprise the 1,3-pentylmethylimidazolium cation ([C(5)mim]+), and the anions, bromide (Br-), hexafluorophosphate (PF(6)-), and bis(trifluoromethanesulfonyl)imide (NTf(2)-). Whereas the optical Kerr effect (OKE) spectrum of [C(5)mim][NTf(2)] is temperature-dependent, the OKE spectra of [C(5)mim]Br and [C(5)mim][PF6] are temperature-independent. These results are surprising in light of the fact that the bulk densities of these room temperature ionic liquids (RTILs) are temperature-dependent. The temperature independence of the OKE spectra and the temperature dependence of the bulk density in [C(5)mim]Br and [C(5)mim][PF(6)] suggest that there are inhomogeneities in the densities of these liquids. The existence of density inhomogeneities is consistent with recent molecular dynamics simulations that show RTILs to be nanostructurally organized with nonpolar regions arising from clustering of the alkyl chains and ionic networks arising from charge ordering of the anions and imidazolium rings of the cations. Differences in the temperature dependences of the OKE spectra are rationalized on the basis of the degree of charge ordering in the polar regions of the RTILs. PMID:17474695

  17. The general AMBER force field (GAFF) can accurately predict thermodynamic and transport properties of many ionic liquids.

    PubMed

    Sprenger, K G; Jaeger, Vance W; Pfaendtner, Jim

    2015-05-01

    We have applied molecular dynamics to calculate thermodynamic and transport properties of a set of 19 room-temperature ionic liquids. Since accurately simulating the thermophysical properties of solvents strongly depends upon the force field of choice, we tested the accuracy of the general AMBER force field, without refinement, for the case of ionic liquids. Electrostatic point charges were developed using ab initio calculations and a charge scaling factor of 0.8 to more accurately predict dynamic properties. The density, heat capacity, molar enthalpy of vaporization, self-diffusivity, and shear viscosity of the ionic liquids were computed and compared to experimentally available data, and good agreement across a wide range of cation and anion types was observed. Results show that, for a wide range of ionic liquids, the general AMBER force field, with no tuning of parameters, can reproduce a variety of thermodynamic and transport properties with similar accuracy to that of other published, often IL-specific, force fields. PMID:25853313

  18. Silver halide fiber-based evanescent-wave liquid droplet sensing with thermoelectrically cooled room temperature mid-infrared quantum cascade lasers

    NASA Astrophysics Data System (ADS)

    Chen, Jian Z.; Liu, Zhijun; Gmachl, Claire F.; Sivco, Deborah L.

    2005-11-01

    Quantum cascade lasers coupled directly to unclad silver halide fibers were used to assemble mid-infrared fiber-optics evanescent-wave sensors suitable to measure the chemical composition of simple liquid droplets. Quantum cascade lasers can be designed to emit across a wide range of mid-infrared wavelengths by tailoring the quantum-well structure, and the wavelength can be fine tuned by a thermoelectric cooler. Here, laser wavelengths were chosen which offer the largest absorption contrast between two constituents of a droplet. The laser was coupled to an unclad silver halide fiber, which penetrates through the droplet resting on a hydrophobic surface. For the same liquid composition and droplet size, the transmitted intensity is weaker for a droplet on a 1H,1H,2H,2H-perfluoro-octyltrichlorosilane coated glass slide than for one on a hexadecanethiol (HDT) coated Au-covered glass slide because of the high reflectivity of the HDT/Au surface at mid-infrared wavelengths. The absorption coefficients of water, glycerol, α-tocophenol acetate, and squalane were measured by varying the immersion length of the fiber; i.e. the droplet size. A pseudo-Beer-Lambert law fits well with the experimental data. We tested both aqueous liquid mixtures (acetone/water and ethanol/water) and oil-base solutions (n-dodecane/squalane and α-tocophenol acetate/squalane); α-tocophenol acetate and squalane are common ingredients of cosmetics, either as active ingredients or for chemical stabilization. Using a 300μm diameter silver halide fiber with a 25mm immersion length, the detection limits are 1 vol.% for α-tocophenol in squalane and 2 vol.% for acetone in water for laser wavenumbers of 1208 cm -1 and 1363 cm -1, respectively. This work was previously been reported in J. Z. Chen et al. Optics Express 13, 5953 (2005).

  19. Room temperature on-surface synthesis of two-dimensional imine polymers at the solid/liquid interface: concentration takes control.

    PubMed

    Yu, Yanxia; Lin, Jianbin; Wang, Yan; Zeng, Qingdao; Lei, Shengbin

    2016-05-01

    Though moderate heating in a controlled environment is generally considered to be necessary, in this work we show that the most important prerequisite for obtaining high quality 2D imine polymers at the interface is the concentration and molar ratio of building blocks on the surface. With diverse monomers we have demonstrated that the concentration-in-control strategy is a general and powerful way to construct covalent single layer 2D imine polymers with high regularity at the solid/liquid interface. PMID:27111697

  20. Adsorption Kinetics at Silica Gel/Ionic Liquid Solution Interface.

    PubMed

    Flieger, Jolanta; Tatarczak-Michalewska, Małgorzata; Groszek, Anna; Blicharska, Eliza; Kocjan, Ryszard

    2015-01-01

    A series of imidazolium and pyridinium ionic liquids with different anions (Cl(-), Br(-), BF₄(-), PF₆(-)) has been evaluated for their adsorption activity on silica gel. Quantification of the ionic liquids has been performed by the use of RP-HPLC with organic-aqueous eluents containing an acidic buffer and a chaotropic salt. Pseudo-second order kinetic models were applied to the experimental data in order to investigate the kinetics of the adsorption process. The experimental data showed good fitting with this model, confirmed by considerably high correlation coefficients. The adsorption kinetic parameters were determined and analyzed. The relative error between the calculated and experimental amount of ionic liquid adsorbed at equilibrium was within 7%. The effect of various factors such as initial ionic liquid concentration, temperature, kind of solvent, kind of ionic liquid anion and cation on adsorption efficiency were all examined in a lab-scale study. Consequently, silica gel showed better adsorptive characteristics for imidazolium-based ionic liquids with chaotropic anions from aqueous solutions in comparison to pyridinium ionic liquids. The adsorption was found to decrease with the addition of organic solvents (methanol, acetonitrile) but it was not sensitive to the change of temperature in the range of 5-40 °C. PMID:26690392

  1. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    SciTech Connect

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center; Institute of Chemistry, Hebrew University; Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Leone, Stephen R.

    2011-07-19

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?]ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources.

  2. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    SciTech Connect

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center; Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; L.Vaghjiani, Ghanshyam; Leone, Stephen R.

    2012-03-16

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1- Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?] ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources.

  3. Chelating ionic liquids for reversible zinc electrochemistry.

    PubMed

    Kar, Mega; Winther-Jensen, Bjorn; Forsyth, Maria; MacFarlane, Douglas R

    2013-05-21

    Advanced, high energy-density, metal-air rechargeable batteries, such as zinc-air, are of intense international interest due to their important role in energy storage applications such as electric and hybrid vehicles, and to their ability to deal with the intermittency of renewable energy sources such as solar and wind. Ionic liquids offer a number of ideal thermal and physical properties as potential electrolytes in such large-scale energy storage applications. We describe here the synthesis and characterisation of a family of novel "chelating" ILs designed to chelate and solubilize the zinc ions to create electrolytes for this type of battery. These are based on quaternary alkoxy alkyl ammonium cations of varying oligo-ether side chains and anions such as p-toluene sulfonate, bis(trifluoromethylsulfonyl)amide and dicyanoamides. This work shows that increasing the ether chain length in the cation from two to four oxygens can increase the ionic conductivity and reduce the melting point from 67 °C to 15 °C for the tosylate system. Changing the anion also plays a significant role in the nature of the zinc deposition electrochemistry. We show that zinc can be reversibly deposited from [N(222(20201))][NTf2] and [N(222(202020201))][NTf2] beginning at -1.4 V and -1.7 V vs. SHE, respectively, but not in the case of tosylate based ILs. This indicates that the [NTf2] is a weaker coordinating anion with the zinc cation, compared to the tosylate anion, allowing the coordination of the ether chain to dominate the behavior of the deposition and stripping of zinc ions. PMID:23558696

  4. How does lithium oxalyldifluoroborate enable the compatibility of ionic liquids and carbon-based capacitors?

    NASA Astrophysics Data System (ADS)

    Chen, Renjie; Chen, Yan; Xu, Bin; Zhang, Rong; He, Zhouying; Wu, Feng; Li, Li

    2015-02-01

    Lithium oxalyldifluoroborate (LiODFB) has several unique characteristics, such as high ionic conductivity over a wide temperature range and the ability to form and stabilize solid electrolyte interface films on graphite surfaces. A series of binary, room-temperature, molten electrolytes composed of LiODFB and organic compounds with acylamino groups (acetamide, oxazolidinone or OZO) have been synthesized. Fourier-transform infrared (FT-IR) spectroscopy indicates that Cdbnd O and N-H functional groups undergo blue or red shifts upon addition of LiODFB. The electrolytes have excellent thermal stabilities and electrochemical characteristics that allow them to be promising electrolytes for electrochemical double layer capacitors (EDLCs). Here, we examine 1:5 molar ratio LiODFB and acetamide/OZO ionic liquid (IL) electrolytes in EDLCs. IL compatibility with two types of carbon-based electrodes is investigated theoretically and experimentally. We simulate possible structures and ion diameters for the ILs, which must be compatible with pore sizes of the carbon electrodes. Mesoporous activated carbon AC2, with a pore size similar to the ionic diameter of LiODFB-acetamide, has a specific capacitance of 154.2 Fg-1 at 20 m Ag-1. Additionally, typical capacitive and reversibility behaviors can be seen in the charge-discharge curves over 0-2 V. Finally, the EDLCs exhibit good charging/discharging performances.

  5. Temperature dependence of the electrical conductivity of imidazolium ionic liquids.

    PubMed

    Leys, Jan; Wübbenhorst, Michael; Preethy Menon, Chirukandath; Rajesh, Ravindran; Thoen, Jan; Glorieux, Christ; Nockemann, Peter; Thijs, Ben; Binnemans, Koen; Longuemart, Stéphane

    2008-02-14

    The electrical conductivities of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids and of 1-hexyl-3-methylimidazolium ionic liquids with different anions were determined in the temperature range between 123 and 393 K on the basis of dielectric measurements in the frequency range from 1 to 10(7) Hz. Most of the ionic liquids form a glass and the conductivity values obey the Vogel-Fulcher-Tammann equation. The glass transition temperatures are increasing with increasing length of the alkyl chain. The fragility is weakly dependent on the alkyl chain length but is highly sensitive to the structure of the anion. PMID:18282058

  6. Temperature dependence of the electrical conductivity of imidazolium ionic liquids

    NASA Astrophysics Data System (ADS)

    Leys, Jan; Wübbenhorst, Michael; Preethy Menon, Chirukandath; Rajesh, Ravindran; Thoen, Jan; Glorieux, Christ; Nockemann, Peter; Thijs, Ben; Binnemans, Koen; Longuemart, Stéphane

    2008-02-01

    The electrical conductivities of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids and of 1-hexyl-3-methylimidazolium ionic liquids with different anions were determined in the temperature range between 123 and 393K on the basis of dielectric measurements in the frequency range from 1to107Hz. Most of the ionic liquids form a glass and the conductivity values obey the Vogel-Fulcher-Tammann equation. The glass transition temperatures are increasing with increasing length of the alkyl chain. The fragility is weakly dependent on the alkyl chain length but is highly sensitive to the structure of the anion.

  7. Triphilic Ionic-Liquid Mixtures: Fluorinated and Non-fluorinated Aprotic Ionic-Liquid Mixtures

    PubMed Central

    Hollóczki, Oldamur; Macchiagodena, Marina; Weber, Henry; Thomas, Martin; Brehm, Martin; Stark, Annegret; Russina, Olga; Triolo, Alessandro; Kirchner, Barbara

    2015-01-01

    We present here the possibility of forming triphilic mixtures from alkyl- and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains—polar and nonpolar—three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self-associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long-range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment. PMID:26305804

  8. Triphilic Ionic-Liquid Mixtures: Fluorinated and Non-fluorinated Aprotic Ionic-Liquid Mixtures.

    PubMed

    Hollóczki, Oldamur; Macchiagodena, Marina; Weber, Henry; Thomas, Martin; Brehm, Martin; Stark, Annegret; Russina, Olga; Triolo, Alessandro; Kirchner, Barbara

    2015-10-26

    We present here the possibility of forming triphilic mixtures from alkyl- and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains-polar and nonpolar-three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self-associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long-range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment. PMID:26305804

  9. Development of Practical Supported Ionic Liquid Membranes: A Systematic Approach

    SciTech Connect

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

    2007-11-01

    Supported liquid membranes (SLMs) are a class of materials that allow the researcher to utilize the wealth of knowledge available on liquid properties to optimize membrane performance. These membranes also have the advantage of liquid phase diffusivities, which are higher than those observed in polymers and grant proportionally greater permeabilities. The primary shortcoming of the supported liquid membranes demonstrated in past research has been the lack of stability caused by volatilization of the transport liquid. Ionic liquids, which may possess high CO2 solubility relative to light gases such as H2, are excellent candidates for this type of membrane since they are stable at elevated temperatures and have negligible vapor pressure. A study has been conducted evaluating the use of a variety of ionic liquids in supported ionic liquid membranes for the capture of CO2 from streams containing H2. In a joint project, researchers at the University of Notre Dame synthesized and characterized ionic liquids, and researchers at the National Energy Technology Laboratory incorporated candidate ionic liquids into supports and evaluated membrane performance for the resulting materials. Several steps have been taken in the development of practical supported ionic liquid membranes. Proof-of-concept was established by showing that ionic liquids could be used as the transport media in SLMs. Results showed that ionic liquids are suitable media for gas transport, but the preferred polymeric supports were not stable at temperatures above 135oC. The use of cross-linked nylon66 supports was found to produce membranes mechanically stable at temperatures exceeding 300oC but CO2/H2 selectivity was poor. An ionic liquid whose selectivity does not decrease with increasing temperature was needed, and a functionalized ionic liquid that complexes with CO2 was used. An increase in CO2/H2 selectivity with increasing temperature over the range of 37 to 85oC was observed and the dominance of a facilitated transport mechanism established. The presentation will detail membrane development, the effect of increasing transmembrane pressure, and preliminary results dealing with other gas pairs and contaminants.

  10. Titanium deposition from ionic liquids - appropriate choice of electrolyte and precursor.

    PubMed

    Berger, Claudia A; Arkhipova, Maria; Farkas, Attila; Maas, Gerhard; Jacob, Timo

    2016-02-01

    In this study titanium isopropoxide was dissolved in 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) and further in a custom-made guanidinium-based ionic liquid (N11N11NpipGuaTFSI). Electrochemical investigations were carried out by means of cyclic voltammetry (CV) and the initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). For BMITFSI we found one large cathodic reduction peak at a potential of -1.2 V vs. Pt, corresponding to the growth of monoatomic high islands. The obtained deposit was identified as elemental titanium by Auger Electron Spectroscopy (AES). Furthermore, we found a corresponding anodic peak at -0.3 V vs. Pt, which is associated with the dissolution of the islands. This observation leads to the assumption that titanium deposition from the imidazolium-based room-temperature ionic liquid (RTIL) proceeds in a one-step electron transfer. In contrast, for the guanidinium-based RTIL we found several peaks during titanium reduction and oxidation, which indicates a multi-step electron transfer in this alternative electrolyte. PMID:26807860

  11. Trace detection of oxygen--ionic liquids in gas sensor design.

    PubMed

    Baltes, N; Beyle, F; Freiner, S; Geier, F; Joos, M; Pinkwart, K; Rabenecker, P

    2013-11-15

    This paper presents a novel electrochemical membrane sensor on basis of ionic liquids for trace analysis of oxygen in gaseous atmospheres. The faradaic response currents for the reduction of oxygen which were obtained by multiple-potential-step-chronoamperometry could be used for real time detection of oxygen down to concentrations of 30 ppm. The theoretical limit of detection was 5 ppm. The simple, non-expensive sensors varied in electrolyte composition and demonstrated a high sensitivity, a rapid response time and an excellent reproducibility at room temperature. Some of them were continuously used for at least one week and first results promise good long term stability. Voltammetric, impedance and oxygen detection studies at temperatures up to 200 °C (in the presence and absence of humidity and CO2) revealed also the limitations of certain ionic liquids for some electrochemical high temperature applications. Application areas of the developed sensors are control and analysis processes of non oxidative and oxygen free atmospheres. PMID:24148432

  12. Heparin-like native protein aggregate dissociation by 1-alkyl-3-methyl imidazolium chloride ionic liquids.

    PubMed

    Rawat, Kamla; Bohidar, H B

    2015-02-01

    At room temperature, ionic liquids (ILs) 1-alkyl-3-methyl imidazolium chloride (alkyl: ethyl, butyl, hexyl and octyl) are observed to exhibit aggregate dissociation behavior of native proteins. This is similar to the well known protein aggregation inhibitor and aggregate dissociation molecule heparin. Dynamic light scattering (DLS) experiments performed on three model proteins bovine serum albumin (BSA), ?-lactoglobulin (?-Lg) and immunoglobulin (IgG) revealed that on addition of ILs the fractal aggregates of proteins (apparent maximum hydrodynamic radius Rmax and fractal dimension df=1.50.2) dissociated into oligomers (hydrodynamic radius Rh) following an exponential decay profile with time, Rh=Rmaxexp(-kat) The dissociation constant ka has been correlated to hydrophobicity index (H-index) of the protein concerned. Thus, if the combined contributions of dissociation constant and hydration effect on secondary structure are taken into account together, [C8mim][Cl] with BSA, [C2mim][Cl] with ?-Lg and IgG, rank as the best aggregation reversal agent (ARA) amongst all other ionic liquid samples examined. The additional advantage of the used ILs over heparin is the release of mobile Cl(-) ions to the solution. This lead to the increased solution entropy, thereby, providing stability to the final dispersions. PMID:25445684

  13. Stable silicon-ionic liquid interface for next-generation lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Piper, Daniela Molina; Evans, Tyler; Leung, Kevin; Watkins, Tylan; Olson, Jarred; Kim, Seul Cham; Han, Sang Sub; Bhat, Vinay; Oh, Kyu Hwan; Buttry, Daniel A.; Lee, Se-Hee

    2015-02-01

    We are currently in the midst of a race to discover and develop new battery materials capable of providing high energy-density at low cost. By combining a high-performance Si electrode architecture with a room temperature ionic liquid electrolyte, here we demonstrate a highly energy-dense lithium-ion cell with an impressively long cycling life, maintaining over 75% capacity after 500 cycles. Such high performance is enabled by a stable half-cell coulombic efficiency of 99.97%, averaged over the first 200 cycles. Equally as significant, our detailed characterization elucidates the previously convoluted mechanisms of the solid-electrolyte interphase on Si electrodes. We provide a theoretical simulation to model the interface and microstructural-compositional analyses that confirm our theoretical predictions and allow us to visualize the precise location and constitution of various interfacial components. This work provides new science related to the interfacial stability of Si-based materials while granting positive exposure to ionic liquid electrochemistry.

  14. Polymerized Ionic Liquids: Promising Class of Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Sokolov, Alexei

    Use of polymer electrolytes instead of traditional liquid electrolytes offers an elegant solution to many problems in current battery technology. However, a major obstacle in use of polymer electrolytes is their low ionic conductivity and low transference number (percentage of charge transported by the desired ion). Polymerized ionic liquids (PolyILs), a relatively new class of polymer electrolytes, are essentially single ion conductors and provide simple solution for the increase of the transference number. However, their ionic conductivity at ambient conditions remains low. Our earlier studies demonstrated that only strong decoupling of ionic conductivity from segmental dynamics can lead to a `superionic' behavior of a polymer and might provide sufficiently high conductivity. Based on this concept, we overview recent developments in the field of polymerized ionic liquids, with the emphasis on the polymer specific decoupling of ionic conductivity from segmental dynamics. The latter is well illustrated by the comparison of ionic liquids with their polymerized analogs. Ways to further improvement of ionic conductivity in PolyILs, and their possible limitations are discussed at the end.

  15. A structural investigation of ionic liquid mixtures.

    PubMed

    Matthews, Richard P; Villar-Garcia, Ignacio J; Weber, Cameron C; Griffith, Jeraime; Cameron, Fiona; Hallett, Jason P; Hunt, Patricia A; Welton, Tom

    2016-03-16

    The structures of mixtures of ionic liquids (ILs) featuring a common 1-butyl-3-methylimidazolium ([C4C1im](+)) cation but different anions have been investigated both experimentally and computationally. (1)H and (13)C NMR of the ILs and their mixtures has been performed both on the undiluted liquids and those diluted by CD2Cl2. These experiments have been complemented by quantum chemical density functional theory calculations and molecular dynamics simulations. These techniques have identified the formation of preferential interactions between H(2) of the imidazolium cation and the most strongly hydrogen bond (H-bond) accepting anion. In addition, a preference for the more weakly H-bond accepting anion to interact above the imidazolium ring through anion-π(+) interactions has been identified. The modelling of these data has identified that the magnitude of these preferences are small, of the order of only a few kJ mol(-1), for all IL mixtures. No clustering of the anions around a specific cation could be observed, indicating that these interactions arise from the reorientation of the cation within a randomly assigned network of anions. π(+)-π(+) stacking of the imidazolium cations was also studied and found to be promoted by ILs with a strong H-bond accepting anion. Stacking interactions are easily disrupted by the introduction of small proportions (<50 mol%) of a weakly coordinating anion due to their propensity to form anion-π(+) interactions. These results suggest that the formation of IL mixtures with different anions leads to subtle structural changes of much lower energy than the Coulombic ordering of ions, accounting for why most IL mixtures exhibit ideal, or nearly ideal, behaviour. PMID:26947103

  16. Borohydride ionic liquids and borane/ionic-liquid solutions as hypergolic fuels with superior low ignition-delay times.

    PubMed

    Li, Songqing; Gao, Haixiang; Shreeve, Jean'ne M

    2014-03-10

    In propellant systems, fuels of choice continue to be hydrazine and its derivatives, even though they comprise a class of acutely carcinogenic and toxic substances which exhibit rather high vapor pressures and require expensive handling procedures and costly safety precautions. Hypergolic ionic liquids tend to have low volatility and high thermal and chemical stability, and often exhibit wide liquid ranges, which could allow the use of these substances as bipropellant fuels under a variety of conditions. A new family of borohydride ionic liquids and borane-ionic-liquid solutions is described which meets nearly all of the desired important criteria for well-performing fuels. They exhibit ignition-delay times that are superior to that of any known hypergolic ionic liquid and may thus be legitimate replacements for hydrazine and its derivatives. PMID:24604814

  17. Biocompatible Ionic Liquid-Derived Conducting Polymers

    NASA Astrophysics Data System (ADS)

    Firestone, Millicent; Burns, Christopher; Lee, Sungwon

    2009-03-01

    A significant and frequently encountered challenge when making an electrical connection to a protein is that its electron-transfer sites are buried within the polypeptide matrix and thus, are not readily accessible to bulk metal electrodes. A further complicating factor is that inorganic (i.e., metallic) electrodes are often incompatible with biological samples. These obstacles might be overcome by the use of conducting oligomers and / or polymers, which are flexible, offering a means to access remote redox centers. These oligomers can be readily modified to include chemical moieties that can connect covalently to sites near redox centers. In addition, conducting polymers can be made to be environmentally responsive (dynamic), processable (conformal coating, soluble) and mechanically durable, thus enabling them to function as an electrical conduit (wire or electrode) to biomolecules. In this work, we describe the design, synthesis and electrochemical properties of thiophene-based ionic liquid monomers and their bulk polymerization by chemical oxidation to yield cationic, aqueous-soluble polymers. Preliminary studies evaluating the electropolymerization of these monomers into nanostructured thin films will also be presented.

  18. Surface modification using ionic liquid ion beams

    NASA Astrophysics Data System (ADS)

    Takaoka, Gikan H.; Hamaguchi, Takuya; Takeuchi, Mitsuaki; Ryuto, Hiromichi

    2014-12-01

    We developed an ionic liquid (IL) ion source using 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) and produced IL ion beams by applying a high electric field between the tip and the extractor. Time-of-flight measurements showed that small cluster and fragment ions were contained in the positive and negative ion beams. The positive and negative cluster ions were deposited on Si(1 0 0) substrates. X-ray photoelectron spectroscopy measurements showed that the composition of the deposited layers was similar to that of an IL solvent. This suggests that a cation (A+) or an anion (B-) was attached to an IL cluster (AB)n, resulting in the formation of positive cluster ions (AB)nA+ or negative cluster ions (AB)nB-, respectively. The surfaces of the IL layers deposited on Si(1 0 0) substrates were flat at an atomic level for positive and negative cluster ion irradiation. Moreover, the contact angles of the deposited layers were similar to that of the IL solvent. Thus, surface modification of Si(1 0 0) substrates was successfully demonstrated with BMIM-PF6 cluster ion beams.

  19. Ionic liquids as plasticizers for polyelectrolyte complexes.

    PubMed

    Zhang, Bodong; Hoagland, David A; Su, Zhaohui

    2015-02-26

    Uptake of salts by insoluble polyelectrolyte complexes (PECs) leads to plasticization, and here it is shown that ionic liquids (ILs) are more effective plasticizers than simple organic salts such as NaCl. The PEC uptake of IL cation was monitored by solution (1)H NMR, and the mechanical impacts of plasticization were tracked by dynamic mechanical analysis (DMA). PECs prepared with polystyrene sulfonate (PSS) and poly(diallyldimethylammonium chloride) (PDDA) under charge stoichiometric conditions were immersed in aqueous solutions of 1-butyl-3-methylimidazolium chloride [BMIM][Cl] to cause IL uptake, which could be controlled by the solution's IL concentration: higher concentration leads to higher uptake which leads to greater plasticization. The effectiveness of plasticization was assessed through the position and height of a DMA tan(δ) peak ascribed to a glassy-to-rubbery PEC transition. Consistent with greater PEC uptake, isothermal titration calorimetry demonstrated that solution binding by PSS of [BMIM](+) was much stronger than binding of Na(+). PMID:25686291

  20. Long-range electrostatic screening in ionic liquids.

    PubMed

    Gebbie, Matthew A; Dobbs, Howard A; Valtiner, Markus; Israelachvili, Jacob N

    2015-06-16

    Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

  1. Long-range electrostatic screening in ionic liquids

    PubMed Central

    Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus; Israelachvili, Jacob N.

    2015-01-01

    Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

  2. Atomistic simulations of the solid-liquid transition of 1-ethyl-3-methyl imidazolium bromide ionic liquid

    NASA Astrophysics Data System (ADS)

    Feng, Haijun; Zhou, Jian; Qian, Yu

    2011-10-01

    Achieving melting point around room temperature is important for applications of ionic liquids. In this work, molecular dynamics simulations are carried out to investigate the solid-liquid transition of ionic liquid 1-ethyl-3-methyl imidazolium bromide ([emim]Br) by direct heating, hysteresis, void-nucleation, sandwich, and microcanonical ensemble approaches. Variations of the non-bonded energy, density, diffusion coefficient, and translational order parameter of [emim]Br are analyzed as a function of temperature, and a coexisting solid-liquid system is achieved in the microcanonical ensemble method. The melting points obtained from the first three methods are 547 ± 8 K, 429 ± 8 K, and 370 ± 6 K; while for the sandwich method, the melting points are 403 ± 4 K when merging along the x-axis by anisotropic isothermal-isobaric (NPT) ensemble, 393 ± 4 K when along the y-axis by anisotropic NPT ensemble, and 375 ± 4 K when along the y-axis by isotropic NPT ensemble. For microcanonical ensemble method, when the slabs are merging along different directions (x-axis, y-axis, and z-axis), the melting points are 364 ± 3 K, 365 ± 3 K, and 367 ± 3 K, respectively, the melting points we get by different methods are approximately 55.4%, 21.9%, 5.1%, 14.5%, 11.6%, 6.5%, 3.4%, 3.7%, and 4.3% higher than the experimental value of 352 K. The advantages and disadvantages of each method are discussed. The void-nucleation and microcanonical ensemble methods are most favorable for predicting the solid-liquid transition.

  3. Experimental and theoretical study of carbohydrate-ionic liquid interactions.

    PubMed

    Hassan, El-Sayed R E; Mutelet, Fabrice; Bouroukba, Mohammed

    2015-08-20

    With increasing interest in the use of lignocellulosic biomass for the production of renewable transportation fuels, new approaches for biomass pretreatment have been of considerable interest. The conversion of biomass cellulose to water-soluble sugars is currently one of the most intensive demands worldwide. The use of ionic liquids has been described as a new potentially viable development in this area. Indeed, previous work indicates that carbohydrates are soluble in some imidazolium based ionic liquids. For a better understanding of the behavior of such systems, theoretical quantum chemical calculation have become complementarities of experimental measurements. The goal of this work is to investigate the fundamental natures of the interaction between glucose or cellulose and imidazolium based ionic liquids using ab initio calculations and comparing these results with experimental data. Furthermore, a characterization study was made to investigate the changes in the cellulose structure during the process of solubility and regeneration with ionic liquids. PMID:25965489

  4. Electropolymerization of polypyrrole by bipolar electrochemistry in an ionic liquid.

    PubMed

    Kong, Shuwei; Fontaine, Olivier; Roche, Jérôme; Bouffier, Laurent; Kuhn, Alexander; Zigah, Dodzi

    2014-03-25

    Bipolar electrochemistry has been recently explored for the modification of conducting micro- and nanoobjects with various surface layers. So far, it has been assumed that such processes should be carried out in low-conductivity electrolytes in order to be efficient. We report here the first bipolar electrochemistry experiment carried out in an ionic liquid, which by definition shows a relatively high conductivity. Pyrrole has been electropolymerized on a bipolar electrode, either in ionic liquid or in acetonitrile. The resulting polymer films were characterized by scanning electron microscopy and by contact profilometry. We demonstrate that the films obtained in an ionic liquid are thinner and smoother than the films synthesized in acetonitrile. Furthermore, a well-defined band of polypyrrole can be obtained in ionic liquid, in contrast to acetonitrile for which the polypyrrole film is present on the whole anodic part of the bipolar electrode. PMID:24605863

  5. DIRECT FORMATION OF TETRAHYDROPYRANOLS VIA CATALYSIS IN IONIC LIQUID

    EPA Science Inventory

    Utilizing a simple homoallyl alcohol and an aldehyde in the presence of a catalytic amount of cerium triflate, the direct formation of tetrahydropyranol derivatives in ionic liquid is reported.

  6. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

    PubMed Central

    Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

    2015-01-01

    Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

  7. The radiation chemistry of ionic liquids: A review

    SciTech Connect

    Mincher, Bruce J.; Wishart, James F.

    2014-07-03

    Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquid radiation chemistry literature as it affects separations, with these considerations in mind.

  8. Robust and versatile ionic liquid microarrays achieved by microcontact printing

    NASA Astrophysics Data System (ADS)

    Gunawan, Christian A.; Ge, Mengchen; Zhao, Chuan

    2014-04-01

    Lab-on-a-chip and miniaturized systems have gained significant popularity motivated by marked differences in material performance at the micro-to-nano-scale realm. However, to fully exploit micro-to-nano-scale chemistry, solvent volatility and lack of reproducibility need to be overcome. Here, we combine the non-volatile and versatile nature of ionic liquids with microcontact printing in an attempt to establish a facile protocol for high throughput fabrication of open microreactors and microfluidics. The micropatterned ionic liquid droplets have been demonstrated as electrochemical cells and reactors for microfabrication of metals and charge transfer complexes, substrates for immobilization of proteins and as membrane-free high-performance amperometric gas sensor arrays. The results suggest that miniaturized ionic liquid systems can be used to solve the problems of solvent volatility and slow mass transport in viscous ionic liquids in lab-on-a-chip devices, thus providing a versatile platform for a diverse number of applications.

  9. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

    PubMed

    Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

    2015-01-01

    Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO?) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO? sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

  10. The magic of aqueous solutions of ionic liquids: ionic liquids as a powerful class of catanionic hydrotropes†

    PubMed Central

    Cláudio, Ana Filipa M.; Neves, Márcia C.; Shimizu, Karina; Canongia Lopes, José N.; Freire, Mara G.; Coutinho, João A. P.

    2015-01-01

    Hydrotropes are compounds able to enhance the solubility of hydrophobic substances in aqueous media and therefore are widely used in the formulation of drugs, cleaning and personal care products. In this work, it is shown that ionic liquids are a new class of powerful catanionic hydrotropes where both the cation and the anion synergistically contribute to increase the solubility of biomolecules in water. The effects of the ionic liquid chemical structures, their concentration and the temperature on the solubility of two model biomolecules, vanillin and gallic acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of these two biomolecules was studied in the entire composition range, from pure water to pure ionic liquids, and an increase in the solubility of up to 40-fold was observed, confirming the potential of ionic liquids to act as hydrotropes. Using dynamic light scattering, NMR and molecular dynamics simulations, it was possible to infer that the enhanced solubility of the biomolecule in the IL aqueous solutions is related to the formation of ionic-liquid–biomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media. PMID:26379471

  11. Room temperature inorganic ``quasi-molten salts`` as alkali-metal electrolytes

    SciTech Connect

    Xu, K.; Zhang, S.; Angell, C.A.

    1996-11-01

    Room temperature inorganic liquids of high ionic conductivity have been prepared by reacting Lewis acid AlCl with sulfonyl chlorides. The mechanism is not clear at this time since a crystal structure study of the 1:1 complex with CH{sub 3}SO{sub 2}Cl (T{sub m} = 30 C) is not consistent with a simple chloride transfer to create AlClO{sub 4}{sup {minus}} anions. The liquid is in a state somewhere between ionic and molecular. A new term quasi-molten salt is adopted to describe this state. A comparably conducting liquid can be made using BCL{sub 3} in place of AlCl{sub 3}. Unlike their organic counterparts based on ammonium cations (e.g., pyridinium or imidazolium) which reduce in the presence of alkali metals, this inorganic class of cation shows great stability against electrochemical reduction (ca. {minus}1.0 V vs. Li{sup +}/Li), with the useful consequence that reversible lithium and sodium metal deposition/stripping can be supported. The electrochemical window for these quasi-salts with AlCl{sub 3} ranges up to 5.0 V, and their room temperature conductivities exceed 10{sup {minus}4} S/cm. They dissolve lithium and sodium tetrachloroaluminates up to mole fraction {approximately} 0.6 at 100 C and intermediate compositions are permanently stable at ambient. The resultant lithium or sodium salt solutions exhibit electrochemical windows of 4.5--5.0 V vs. Li{sup +}/Li or Na{sup +}/Na and show room temperature conductivities of 10{sup {minus}3.0}--10{sup {minus}2.5} S/cm. In preliminary charge/discharge tests, the cell Li/``quasi-ionic liquid electrolyte``/Li{sub 1+x}Mn{sub 2}O{sub 4} showed a discharge capacity of ca. 110 mAh/(g of cathode) and sustained 80% of the initial capacity after 60 cycles, indicating that these quasi-molten salt-based electrolytes are promising candidates for alkali-metal batteries.

  12. Membrane contactor assisted extraction/reaction process employing ionic liquids

    DOEpatents

    Lin, Yupo J.; Snyder, Seth W.

    2012-02-07

    The present invention relates to a functionalized membrane contactor extraction/reaction system and method for extracting target species from multi-phase solutions utilizing ionic liquids. One preferred embodiment of the invented method and system relates to an extraction/reaction system wherein the ionic liquid extraction solutions act as both extraction solutions and reaction mediums, and allow simultaneous separation/reactions not possible with prior art technology.

  13. Magnetic field tunable capacitive dielectric:ionic-liquid sandwich composites

    NASA Astrophysics Data System (ADS)

    Wu, Ye; Bhalla, Amar; Guo, Ruyan

    2016-03-01

    We examined the tunability of the capacitance for GaFeO3-ionic liquid-GaFeO3 composite material by external magnetic and electric field. Up to 1.6 folds of capacitance tunability could be achieved at 957 kHz with voltage 4 V and magnetic field 0.02 T applied. We show that the capacitance enhancement is due to the polarization coupling between dielectric layer and ionic liquid layer.

  14. NMR spectroscopy to follow reaction progress in ionic liquids.

    PubMed

    Butler, Bradley J; Thomas, Donald S; Hook, James M; Harper, Jason B

    2016-06-01

    In order to understand reaction outcomes in ionic liquids, it is crucial to be able to follow the progress of these reactions. This review highlights the advantages of NMR spectroscopy over other analytical techniques in following reaction progress in ionic liquids, particularly addressing the practical aspects of the methodology and highlighting the range of processes that can be readily followed. Copyright © 2014 John Wiley & Sons, Ltd. PMID:25287592

  15. Ionic liquid propellants: future fuels for space propulsion.

    PubMed

    Zhang, Qinghua; Shreeve, Jean'ne M

    2013-11-11

    Use of green propellants is a trend for future space propulsion. Hypergolic ionic liquid propellants, which are environmentally-benign while exhibiting energetic performances comparable to hydrazine, have shown great potential to meet the requirements of developing nontoxic high-performance propellant formulations for space propulsion applications. This Concept article presents a review of recent advances in the field of ionic liquid propellants. PMID:24136866

  16. Permeability of Rubbery and Glassy Membranes of Ionic Liquid Filled Polymersome Nanoreactors in Water.

    PubMed

    So, Soonyong; Yao, Letitia J; Lodge, Timothy P

    2015-12-01

    Nanoemulsion-like polymer vesicles (polymersomes) having ionic liquid interiors dispersed in water are attractive for nanoreactor applications. In a previous study, we demonstrated that small molecules could pass through rubbery polybutadiene membranes on a time scale of seconds, which is practical for chemical transformations. It is of interest to determine how sensitive the rate of transport is to temperature, particularly for membranes in the vicinity of the glass transition (Tg). In this work, the molecular exchange rate of 1-butylimidazole through glassy polystyrene (PS) bilayer membranes is investigated via pulsed field gradient nuclear magnetic resonance (PFG-NMR) over the temperature range from 25 to 70 °C. The vesicles were prepared by the cosolvent method in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([EMIM][TFSI]), and four different polystyrene-b-poly(ethylene oxide) (PS-PEO) diblock polymers with varying PS molecular weights were examined. The vesicles were transferred from the ionic liquid to water at room temperature to form nanoemulsion solutions of polymer vesicles in water. The exchange rate of 1-butylimidazole added to the aqueous solutions was observed under equilibrium conditions at each temperature. The exchange rate decreased as the membrane thickness increased, and the exchange rate through the glassy membranes was three to four times slower than through the rubbery polybutadiene membranes under the same experimental conditions. These results demonstrate that the permeability through nanosized membranes depends on both the dimension and chemistry of membrane-forming blocks. Furthermore, the exchange rate was investigated as a function of temperature in the vicinity of the Tg of PS-PEO membranes. The exchange rate, however, is not a strong function of the temperature in the vicinity of the membrane Tg, due to a combination of the nanoscopic dimension of the membrane, and some degree of solvent plasticization. PMID:26588106

  17. How is charge transport different in ionic liquids and electrolyte solutions?

    PubMed

    Kashyap, Hemant K; Annapureddy, Harsha V R; Raineri, Fernando O; Margulis, Claudio J

    2011-11-17

    In this article we show that, analyzed in a barycentric reference frame, the deviation in conductivity measured directly from impedance experiments with respect to that estimated indirectly from NMR diffusion experiments has different origins in electrolyte solutions and pure salts. In the case of electrolyte solutions, the momentum conservation law is satisfied by solvent + ions. Instead, in a molten salt or ionic liquid momentum conservation must be satisfied solely by the ions. This has significant implications. While positively correlated motion of ions of opposite charge is a well justified explanation for the reduction in impedance conductivity in the case of electrolyte solutions, it is not so in the case of ionic liquids and molten salts. This work presents a set of equations that in the case of ionic liquids and molten salts can be used to obtain from direct measurements of impedance and NMR the distinct part of the diffusion coefficient matrix in the barycentric reference frame. In other words, by using experimentally measurable quantities, these equations allow us to access the motional coupling between ions for which there is no single direct experimental measurement technique. While equations of this type have been proposed before, the ones presented here can be easily derived from the momentum conservation law and linear response theory. Our results indicate that the decrease in the impedance conductivity with respect to NMR conductivity in ionic liquids and molten salts is due to anticorrelated motion of ions of same charge. This scenario is different in electrolyte solutions, where the positively correlated motion of ions of opposite charge makes a significant contribution to the decrease in the impedance conductivity. In contrast, in a system comprising a single binary salt (a room temperature ionic liquid or a molten salt), the cation-anion distinct diffusion coefficient is negative definite and opposes the contribution from the cation-cation and anion-anion distinct diffusion coefficients. This property of the cation-anion distinct diffusion coefficient in systems comprising just two ion-constituents holds true not just in the barycentric reference frame but also in any of the internal reference frames of nonequilibrium thermodynamics. PMID:22022889

  18. Ionic liquids and electrochemistry: from proteins to electrochromic devices.

    SciTech Connect

    Keizer, T. S.; McCleskey, T. M.; Baker, G. A.; Burrell, A. K.; Baker, S. N.; Warner, B. P.; Hall, S. B.

    2004-01-01

    We will report on a wide range of activities within the chemistry division at Los Alamos National Laboratory. Results on basic and applied research involving electrochemistry will be discussed. Topics will include electrochemistry of proteins, sensors based on electrochemical signals, temperature sensors, electrochromic devices in ionic liquids and the characterization of organic cation radicals. We have recently developed several applications in ionic liquids that include electrochromic devices, temperature sensors and chemical sensors. The electrochromic windows are being marketed as selftinting automotive mirrors. The ionic liquid based temperature sensor is stable and accurate over a wide range and has the potential to provide high-resolution temperature imaging. Chemical sensors have been developed that use electrochemistry to detect low levels of potential chemical agents in air. We have also studied the basic chemistry of charge transfer complexes and proteins in ionic liquids. Charge transfer complexes display unique behavior in ionic liquid compare to traditional solvents. Proteins can be solubilized at high levels that make it possible to probe electrochemistry in the proper ionic liquid.

  19. Thallium Transfer from Hydrochloric Acid Media into Pure Ionic Liquids.

    PubMed

    Tereshatov, Evgeny E; Boltoeva, Maria Yu; Mazan, Valerie; Volia, Merinda F; Folden, Charles M

    2016-03-10

    Pure hydrophobic ionic liquids are known to extract metallic species from aqueous solutions. In this work we have systematically investigated thallium (Tl) extraction from aqueous hydrochloric acid (HCl) solutions into six pure fluorinated ionic liquids, namely imidazolium- and pyrrolidinium-based ionic liquids with bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)-imide anions. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. Tl concentrations were on the order of picomolar (analyzed using radioactive tracers) and millimolar (analyzed using inductively coupled plasma mass spectrometry). The extraction of the cationic thallium species Tl(+) is higher for ionic liquids with more hydrophilic cations, while for the TlXz(3-z) anionic species (where X = Cl(-) and/or Br(-)), the extraction efficiency is greater for ionic liquids with more hydrophobic cations. The highest distribution value of Tl(III) was approximately 2000. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the coextraction of two different anionic species, and the relative contributions of each mechanism have been determined. PMID:26769597

  20. Employing ionic liquids to deposit cellulose on PET fibers.

    PubMed

    Textor, Torsten; Derksen, Leonie; Gutmann, Jochen S

    2016-08-01

    Several ionic liquids are excellent solvents for cellulose. Starting from that finishing of PET fabrics with cellulose dissolved in ionic liquids like 1-ethyl-3-methyl imidazolium acetate, diethylphosphate and chloride, or the chloride of butyl-methyl imidazolium has been investigated. Finishing has been carried out from solutions of different concentrations, using microcrystalline cellulose or cotton and by employing different cross-linkers. Viscosity of solutions has been investigated for different ionic liquids, concentrations, cellulose sources, linkers and temperatures. Since ionic liquids exhibit no vapor pressure, simple pad-dry-cure processes are excluded. Before drying the ionic liquid has to be removed by a rinsing step. Accordingly rinsing with fresh ionic liquid followed by water or the direct rinsing with water have been tested. The amount of cellulose deposited has been investigated by gravimetry, zinc chloride iodine test as well as reactive dyeing. Results concerning wettability, water up-take, surface resistance, wear-resistance or washing stability are presented. PMID:27112860

  1. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

  2. Flow-induced voltage generation by moving a nano-sized ionic liquids droplet over a graphene sheet: Molecular dynamics simulation.

    PubMed

    Shao, Qunfeng; Jia, Jingjing; Guan, Yongji; He, Xiaodong; Zhang, Xiaoping

    2016-03-28

    In this work, the phenomenon of the voltage generation is explored by using the molecular dynamics simulations, which is performed by driving a nano-sized droplet of room temperature ionic liquids moving along the monolayer graphene sheet for the first time. The studies show that the cations and anions of the droplet will move with velocity nonlinearly increasing to saturation arising by the force balance. The traditional equation for calculating the induced voltage is developed by taking the charge density into consideration, and larger induced voltages in μV-scale are obtained from the nano-size simulation systems based on the ionic liquids (ILs) for its enhanced ionic drifting velocities. It is also derived that the viscosity acts as a reduction for the induced voltage by comparing systems composed of two types of ILs with different viscosity and temperature. PMID:27036471

  3. Flow-induced voltage generation by moving a nano-sized ionic liquids droplet over a graphene sheet: Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Shao, Qunfeng; Jia, Jingjing; Guan, Yongji; He, Xiaodong; Zhang, Xiaoping

    2016-03-01

    In this work, the phenomenon of the voltage generation is explored by using the molecular dynamics simulations, which is performed by driving a nano-sized droplet of room temperature ionic liquids moving along the monolayer graphene sheet for the first time. The studies show that the cations and anions of the droplet will move with velocity nonlinearly increasing to saturation arising by the force balance. The traditional equation for calculating the induced voltage is developed by taking the charge density into consideration, and larger induced voltages in μV-scale are obtained from the nano-size simulation systems based on the ionic liquids (ILs) for its enhanced ionic drifting velocities. It is also derived that the viscosity acts as a reduction for the induced voltage by comparing systems composed of two types of ILs with different viscosity and temperature.

  4. Ionic structure in liquids confined by dielectric interfaces

    NASA Astrophysics Data System (ADS)

    Jing, Yufei; Jadhao, Vikram; Zwanikken, Jos W.; Olvera de la Cruz, Monica

    2015-11-01

    The behavior of ions in liquids confined between macromolecules determines the outcome of many nanoscale assembly processes in synthetic and biological materials such as colloidal dispersions, emulsions, hydrogels, DNA, cell membranes, and proteins. Theoretically, the macromolecule-liquid boundary is often modeled as a dielectric interface and an important quantity of interest is the ionic structure in a liquid confined between two such interfaces. The knowledge gleaned from the study of ionic structure in such models can be useful in several industrial applications, such as in the design of double-layer supercapacitors for energy storage and in the extraction of metal ions from wastewater. In this article, we compute the ionic structure in a model system of electrolyte confined by two planar dielectric interfaces using molecular dynamics simulations and liquid state theory. We explore the effects of high electrolyte concentrations, multivalent ions, dielectric contrasts, and external electric field on the ionic distributions. We observe the presence of non-monotonic ionic density profiles leading to a layered structure in the fluid which is attributed to the competition between electrostatic and steric (entropic) interactions. We find that thermal forces that arise from symmetry breaking at the interfaces can have a profound effect on the ionic structure and can oftentimes overwhelm the influence of the dielectric discontinuity. The combined effect of ionic correlations and inhomogeneous dielectric permittivity significantly changes the character of the effective interaction between the two interfaces.

  5. Carbon Dioxide Separation with Supported Ionic Liquid Membranes

    SciTech Connect

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

    2007-04-01

    Supported liquid membranes are a class of materials that allow the researcher to utilize the wealth of knowledge available on liquid properties as a direct guide in the development of a capture technology. These membranes also have the advantage of liquid phase diffusivities higher than those observed in polymeric membranes which grant proportionally greater permeabilities. The primary shortcoming of the supported liquid membranes demonstrated in past research has been the lack of stability caused by volatilization of the transport liquid. Ionic liquids, which possess high carbon dioxide solubility relative to light gases such as hydrogen, are an excellent candidate for this type of membrane since they have negligible vapor pressure and are not susceptible to evaporation. A study has been conducted evaluating the use of several ionic liquids, including 1-hexyl-3-methyl-imidazolium bis(trifuoromethylsulfonyl)imide, 1-butyl-3-methyl-imidazolium nitrate, and 1-ethyl-3-methyl-imidazolium sulfate in supported ionic liquid membranes for the capture of carbon dioxide from streams containing hydrogen. In a joint project, researchers at the University of Notre Dame lent expertise in ionic liquid synthesis and characterization, and researchers at the National Energy Technology Laboratory incorporated candidate ionic liquids into supports and evaluated the resulting materials for membrane performance. Initial results have been very promising with carbon dioxide permeabilities as high as 950 barrers and significant improvements in carbon dioxide/hydrogen selectivity over conventional polymers at 37C and at elevated temperatures. Results include a comparison of the performance of several ionic liquids and a number of supports as well as a discussion of innovative fabrication techniques currently under development.

  6. Fabrication of a new electrochemiluminescent sensor for fentanyl citrate based on glassy carbon microspheres and ionic liquid composite paste electrode.

    PubMed

    Dai, Hong; Xu, Huifeng; Wu, Xiaoping; Chi, Yuwu; Chen, Guonan

    2009-08-01

    Due to the high performance of glassy carbon in the aspects of mechanical strength, electrical conductivity and high corrosion resistance, etc., glassy carbon has been widely used in the electrochemistry. A new form of glassy carbon, glassy carbon microsphere, was utilized to couple with ionic liquid in preparing a new electrochemiluminescent platform for Ru(bpy)3Cl2. Room temperature ionic liquid has been proposed to be very interesting and efficient pasting binder to replace the non conductive organic binders for the fabrication of composite paste electrode. Attributed to the special characteristics of glassy carbon microspheres and room temperature ionic liquid [N-octylpyridium tetrafluoroborate (OPFP)], this new electrochemiluminescent sensor exhibited excellent electrochemiluminescent performance in Ru(bpy)(3)(2+) solution. We first found that fentanyl citrate could increase the ECL of Ru(bpy)(3)(2+), hence an ECL approach was developed for the determination of fentanyl citrate based on this glassy carbon microspheres based electrochemiluminescent platform with high sensitivity. Under the optimized conditions, the enhanced electrochemiluminescent intensity versus fentanyl citrate concentration was linear in the range of 1.0 x 10(-8) to 1.0 x 10(-4) mol L(-1) with a detection limit of 8.5 x 10(-9) mol L(-1), and the relative standard deviation for 1.0 x 10(-6) mol L(-1) fentanyl citrate was 1.90% (n = 10). This protocol has extended the application scopes of glassy carbon material and promoted the application of glassy carbon microspheres in electroanalysis. PMID:19576386

  7. Electron spin-lattice relaxation mechanisms of nitroxyl radicals in ionic liquids and conventional organic liquids: temperature dependence of a thermally activated process.

    PubMed

    Kundu, Krishnendu; Kattnig, Daniel R; Mladenova, Boryana Y; Grampp, Gnter; Das, Ranjan

    2015-03-26

    During the past two decades, several studies have established a significant role played by a thermally activated process in the electron spin relaxation of nitroxyl free radicals in liquid solutions. Its role has been used to explain the spin relaxation behavior of these radicals in a wide range of viscosities and microwave frequencies. However, no temperature dependence of this process has been reported. In this work, our main aim was to investigate the temperature dependence of this process in neat solvents. Electron spin-lattice relaxation times of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-hydroxy-TEMPO (TEMPOL), in X-band microwave frequency, were measured by the pulse saturation recovery technique in three room-temperature ionic liquids ([bmim][BF4], [emim][BF4], and [bmim][PF6]), di-isononyl phthalate, and sec-butyl benzene. The ionic liquids provided a wide range of viscosity in a modest range of temperature. An auxiliary aim was to examine whether the dynamics of a probe molecule dissolved in ionic liquids was different from that in conventional molecular liquids, as claimed in several reports on fluorescence dynamics in ionic liquids. This was the reason for the inclusion of di-isononyl phthalate, whose viscosities are similar to that of the ionic liquids in similar temperatures, and sec-butyl benzene. Rotational correlation times of the nitroxyl radicals were determined from the hyperfine dependence of the electron paramagnetic resonance (EPR) line widths. Observation of highly well-resolved proton hyperfine lines, riding over the nitrogen hyperfine lines, in the low viscosity regime in all the solvents, gave more accurate values of the rotational correlation times than the values generally measured in the absence of these hyperfine lines and reported in the literature. The measured rotational correlation times obeyed a modified Stokes-Einstein-Debye relation of temperature dependence in all solvents. By separating the contributions of g-anisotropy, A-anisotropy and spin-rotation interactions from the observed electron spin-lattice relaxation rates, the contribution of the thermally activated process was obtained and compared with its expression for the temperature dependence. Consistent values of various fitted parameters, used in the expression of the thermal process, have been found, and the applicability of the expression of the thermally activated process to describe the temperature dependence in liquid solutions has been vindicated. Moderate solvent dependence of the thermally activated process has also been observed. The rotational correlation times and the spin-lattice relaxation processes of nitroxyls in ionic liquids and in conventional organic liquids are shown to be explicable on a similar footing, requiring no special treatment for ionic liquids. PMID:25775000

  8. The radiation chemistry of ionic liquids: A review

    DOE PAGESBeta

    Mincher, Bruce J.; Wishart, James F.

    2014-07-03

    Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquidmore » radiation chemistry literature as it affects separations, with these considerations in mind.« less

  9. Nonlinear capacitance and electrochemical response of ionic liquid-ionic polymers

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Goulbourne, N. C.

    2011-04-01

    In this paper we present a physics-based model for the electrochemical response of ionic liquid-ionic polymer transducers (IPTs) and show how the mobile ionic liquid ions influence the charging characteristics and actuation performance of a device. It is assumed that a certain fraction of the ionic liquid ions exist as "free," making for a total of 3 mobile ions. This leads to predictions of distinctly different charging characteristics for ionic liquid versus water-based IPTs, since for the latter there is only a single mobile ion. The large ionic liquid ions are modeled by including steric effects in a set of modified Nernst-Planck/Poisson equations, and the resulting system of equations is solved using the method of matched asymptotic expansions (MAE). The inclusion of steric effects allows for a realistic description of boundary layer composition near actuator operating voltages (~1 V). Analytical expressions for the charge transferred and differential capacitance are derived as a function of the fraction of free ionic liquid ions, influence of steric effects in formation of the electric double layer, and applied voltage. It is shown that the presence of free ionic liquid ions tends to increase the overall amount of charge transferred, and also leads to a nonmonotonic capacitance-voltage curve. We suggest that these results could be used to experimentally identify the extent of free ionic liquid ion movement and to test the validity of the assumptions made in the underlying theory. A comparison with numerical results shows that while the MAE solution procedure gives valid results for capacitance and charge transferred, it cannot predict the dynamic response due to the presence of multiple time scales in the current decay. This is in contrast to previous results in analyzing water-based IPTs, where the MAE solution is in good agreement with numerical results at all times and applied voltages due to the presence of only a single mobile ion. By examining the structure of the electric double layer in the ionic liquid IPT, it is shown that although the additional mobile ions lead to more charge transferred, they likely do not increase the bending moment generated by a cantilevered IPT because of the increase in symmetry in boundary layer charge density profiles. These results are in good qualitative agreement with recent experiments.

  10. The influence of water on the structural and transport properties of model ionic liquids

    NASA Astrophysics Data System (ADS)

    Spohr, Heidrun V.; Patey, G. N.

    2010-06-01

    Molecular dynamics simulations are used to investigate the influence of water on model ionic liquids. Several models, where the ions vary in size, and in the location of the charge with respect to the center of mass, are considered. Particular attention is focused on the variation in transport properties (diffusion coefficients, shear viscosity, and electrical conductivity) with water concentration. An effort is made to identify the underlying physical reasons for water's influence. The results for our model ionic liquids fall loosely into two categories, depending on the molecular characteristics of the constituent ions. If the ion size disparity is not too large (cation:anion diameter ratio≲2:1), and if the ion charge location is such that directional ion pair bonds are relatively weak, then we find that the ionic diffusion coefficients and the electrical conductivity increase, and the viscosity decreases with increasing water concentration. This agrees with what is commonly observed experimentally for room temperature ionic liquids (RTILs). For these systems, we do not find changes in the equilibrium structure that can account for the strong influence of water on the transport properties. Rather, by varying the molecular mass of water in our simulations, we demonstrate that the dominant effect of water can be dynamical in origin. In RTIL-water mixtures, the molecular mass of water is generally much less than that of the ions it replaces. These lighter water molecules tend to displace much heavier counterions from the ion coordination shells. This reduces caging and increases the diffusivity, which leads to higher conductivities and lower viscosities. For models with a larger ion size disparity (3:1), or in charge-off-center systems, where strong directional ion pairs are important in the pure ionic liquid, the behavior can be quite different. In these systems, the diffusion coefficients and electrical conductivity can still display conventional behavior and increase when water is added even though the reasons for this can be more complex than in the simpler cases noted above. However, in these systems the viscosity can increase, sometimes quite steeply, with increasing water concentration. We trace this unusual behavior to the formation of associated structures, extended anion-water chains that can weave among the cations in the size disparate case, and strongly bound cation-water-anion clusters in the charge-off-center systems.

  11. Method and apparatus using an active ionic liquid for algae biofuel harvest and extraction

    DOEpatents

    Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

    2012-11-06

    The invention relates to use of an active ionic liquid to dissolve algae cell walls. The ionic liquid is used to, in an energy efficient manner, dissolve and/or lyse an algae cell walls, which releases algae constituents used in the creation of energy, fuel, and/or cosmetic components. The ionic liquids include ionic salts having multiple charge centers, low, very low, and ultra low melting point ionic liquids, and combinations of ionic liquids. An algae treatment system is described, which processes wet algae in a lysing reactor, separates out algae constituent products, and optionally recovers the ionic liquid in an energy efficient manner.

  12. Polymeric ionic liquid-plastic crystal composite electrolytes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Zhang, Zhengxi; Li, Sijian; Yang, Li; Hirano, Shin-ichi

    2016-03-01

    In this work, composite polymer electrolytes (CPEs), that is, 80%[(1-x)PIL-(x)SN]-20%LiTFSI, are successfully prepared by using a pyrrolidinium-based polymeric ionic liquid (P(DADMA)TFSI) as a polymer host, succinonitrile (SN) as a plastic crystal, and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a lithium salt. XRD and DSC measurements confirm that the as-obtained CPEs have amorphous structures. The 80%[50%PIL-50%SN]-20%LiTFSI (50% SN) electrolyte reveals a high room temperature ionic conductivity of 5.74 × 10-4 S cm-1, a wide electrochemical window of 5.5 V, as well as good mechanical strength with a Young's modulus of 4.9 MPa. Li/LiFePO4 cells assembled with the 50% SN electrolyte at 0.1C rate can deliver a discharge capacity of about 150 mAh g-1 at 25 °C, with excellent capacity retention. Furthermore, such cells are able to achieve stable discharge capacities of 131.8 and 121.2 mAh g-1 at 0.5C and 1.0C rate, respectively. The impressive findings demonstrate that the electrolyte system prepared in this work has great potential for application in lithium ion batteries.

  13. When do defectless alkanethiol SAMs in ionic liquids become penetrable? A molecular dynamics study.

    PubMed

    Kislenko, Sergey A; Nikitina, Victoria A; Nazmutdinov, Renat R

    2015-12-21

    Molecular dynamics simulations were performed to address the permeability of defectless alkanethiol self-assembled monolayers (SAMs) on charged and uncharged Au(111) surfaces in 1-butyl-3-methylimidazolium ([bmim][BF4]) room-temperature ionic liquid (IL). We demonstrate that ionic permeation into the monolayer does not start until a critical surface charge density value is attained (both for positive and negative surface charges). The free energy barrier for the permeation of IL components is shown to include nearly equal contributions from ion desolvation and the channel formation in the dense monolayer. Long chain alkanethiols (hexadecanethiol SC16H33) exhibit superior barrier properties as compared with short chain alkanethiols (hexanethiol SC6H13) due to the dense packing of alkanethiol chains in highly ordered zigzag conformation oriented at the same tilt angle. Computed critical charge densities correspond to the electrode potential values beyond the limits of the monolayer stability, which might indicate the impermeability of the defectless monolayer towards the IL components. Experimental findings on increased interfacial capacitance are interpreted, therefore as some manifestation of the monolayer defectiveness occurring in real electrochemical systems. The potential of the mean force is constructed for a typical redox probe ferrocene/ferrocenium (Fc/Fc(+)) as well, to investigate a possible permeation of the solute from the IL into the SC6H13 monolayer. PMID:26568158

  14. Raidiation-Induced Fragmentation of Diamide Extraction Agents in Ionic Liquid Diluents

    SciTech Connect

    Bell, Jason R; Dai, Sheng; Shkrob, Ilya A.; Marin, Timothy W.; Luo, Huimin; Hatcher, Jasmine; Rimmer, R. Dale; Wishart, James F.

    2012-01-01

    N,N,N',N'-Tetraalkyldiglycolamides are extracting agents that are used for liquid-liquid extraction of trivalent metal ions in wet processing of spent nuclear fuel. This application places such agents in contact with the decaying radionuclides, causing radiolysis of the agent in the organic diluent. Recent research seeks to replace common molecular diluents (such as n-dodecane) with hydrophobic room-temperature ionic liquids (ILs), which have superior solvation properties. In alkane diluents, rapid radiolytic deterioration of diglycolamide agents can be inhibited by addition of an aromatic cosolvent that scavenges highly reactive alkane radical cations before these oxidize the extracting agent. Do aromatic ILs exhibit a similar radioprotective effect? To answer this question, we used electron paramagnetic resonance spectroscopy to study the fragmentation pathways in radiolysis of neat diglycolamides, their model compounds, and their solutions in the ILs. Our study indicates that aromatic ILs do not protect these types of solutes from extensive radiolytic damage. Previous research indicated a similar lack of protection for crown ethers, whereas the ILs readily protected di- and trialkyl phosphates (another large class of metal-extracting agents). Our analysis of these unanticipated failures suggests that new types of organic anions are required in order to formulate ILs capable of radioprotection for these classes of solutes. This study is a cautionary tale of the fallacy of analogical thinking when applied to an entirely new and insufficiently understood class of chemical materials.

  15. Mixed ionic liquids: the case of pyridinium-based fluids.

    PubMed

    Aparicio, Santiago; Atilhan, Mert

    2012-03-01

    We report in this work a combined experimental and computational study on the molecular level structuring of binary ionic liquid mixtures comprising pyridium cations. The effect of anions on liquid structure was analyzed from the mixing (mixture 1) of [b3mpy][BF(4)] and [b3mpy][N(CN)(2)] ionic liquids, in the full composition range, leading to [b3mpy][BF(4)](x)[N(CN)(2)](1-x) mixed ionic liquids. The effect of the length of alkylic chains in cations was studied with mixtures (mixture 2) of [b3mpy][BF(4)] and [o3mpy][BF(4)] ionic liquids, also studied in the full composition range, leading to [b3mpy](x)[o3mpy](1-x)[BF(4)] ionic liquids. Fourier transform infrared-attenuated total reflection spectra were recorded and analyzed as a function of anionic and cationic composition for the two studied mixture types. Classical molecular dynamics simulations were also performed for mixtures 1 and 2 as a function of anionic and cationic composition. The reported experimental and computational results show that the properties of the studied mixed systems change in an almost linear way, leading to almost ideal mixtures from the thermodynamic viewpoint, and thus pointing to simple dilution effects of the involved ions controlling the mixture properties. PMID:22309042

  16. Conductivity of ionic liquid-derived polymers with internal gold nanoparticle conduits.

    SciTech Connect

    Lee, S.; Cummins, M. D.; Willing, G. A.; Firestone, M. A.; Materials Science Division; Univ. of Louisville

    2009-01-01

    The transport properties of self-supporting Au nanoparticle-ionic liquid-derived polymer composites were characterized. Topographic AFM images confirm the perforated lamellar composite architecture determined by small-angle X-ray scattering (SAXS) and further show that the in situ synthesized Au nanoparticles are localized within the hydrophilic (water) domains of the structure. At low Au nanoparticle content, the images reveal incomplete packing of spherical particles (i.e., voids) within these columns. The confinement and organization of the Au nanoparticles within the hydrophilic columns give rise to a large manifold of optical resonances in the near-IR region. The bulk composite conductivity, R{sub b}, was determined by ac electrochemical impedance spectroscopy (EIS) for samples prepared with increasing Au{sup 3+} content over a frequency range of 10 Hz to 1 MHz. A 100-fold increase was observed in the bulk conductivity at room temperature for composites prepared with the highest amount of Au{sup 3+} (1.58 {+-} 0.065 {micro}mol) versus the no Au composite, with the former reaching a value of 1.3 x 10{sup -4} S cm{sup -1} at 25 C. The temperature dependence of the conductivity recorded over this range was well-modeled by the Arrhenius equation. EIS studies on samples containing the highest Au nanoparticle content over a broader range of frequencies (2 x 10{sup -2} Hz to 5 x 10{sup 5} Hz) identified a low frequency component ascribed to electronic conduction. Electronic conduction due to aggregated Au nanoparticles was further confirmed by dc conductivity measurements. This work identifies a nanostructured composite that exhibits both ionic transport through the polymeric ionic liquid and electronic conduction from the organized encapsulated columns of Au nanoparticles.

  17. Efficient dehydration of glucose to 5-hydroxymethylfurfural catalyzed by the ionic liquid,1-hydroxyethyl-3-methylimidazolium tetrafluoroborate.

    PubMed

    Qu, Yongshui; Huang, Chongpin; Song, Yanlei; Zhang, Jie; Chen, Biaohua

    2012-10-01

    The dehydration of fructose or glucose to 5-hydroxymethylfurfural (5-HMF) using room temperature ionic liquids (ILs) as a solvent is a promising method for producing liquid fuels from renewable resources. The IL, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate ([C(2)OHMIM]BF(4)), was used a catalyst-rather than as a solvent-in the conversion of fructose or glucose to 5-HMF. With glucose, the yield of 5-HMF reached as high as 67.3% after 1h at 180°C in dimethylsulfoxide (DMSO) as solvent. The catalyst was separated from the reaction mixture by distilling solvent and reused six times without loss of activity. Furthermore, a kinetic analysis was carried out to illustrate the formation of 5-HMF, and the values of the activation energy and the pre-exponential factor for the reaction were 55.77 kJ mol(-1) and 1.6 × 10(4)min(-1) respectively. PMID:22863180

  18. Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

    NASA Astrophysics Data System (ADS)

    Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

    2013-05-01

    The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

  19. Excess dielectron in an ionic liquid as a dynamic bipolaron.

    PubMed

    Liu, Jinxiang; Wang, Zhiping; Zhang, Meng; Cukier, Robert I; Bu, Yuxiang

    2013-03-01

    We report an ab initio molecular dynamics simulation study on the accommodation of a dielectron in a pyridinium ionic liquid in both the singlet and triplet state. In contrast to water and liquid ammonia, a dielectron does not prefer to reside in cavity-shaped structures in the ionic liquid. Instead, it prefers to be distributed over more cations, with long-lived diffuse and short-lived localized distributions, and with a triplet ground state and a low-lying, open-shell singlet excited state. The two electrons evolve nonsynchronously in both states via a diffuse-versus-localized interconversion mechanism that features a dynamic bipolaron with a modest mobility, slightly lower than a hydrated electron. This work presents the first detailed study on the structures and dynamics of a dielectron in ionic liquids. PMID:23521297

  20. Molecular solutes in ionic liquids: a structural perspective.

    PubMed

    Pádua, Agílio A H; Costa Gomes, Margarida F; Canongia Lopes, José N A

    2007-11-01

    Understanding physicochemical properties of ionic liquids is important for their rational use in extractions, reactions, and other applications. Ionic liquids are not simple fluids: their ions are generally asymetric, flexible, with delocalized electrostatic charges, and available in a wide variety. It is difficult to capture their subtle properties with models that are too simplistic. Molecular simulation using atomistic force fields, which describe structures and interactions in detail, is an excellent tool to gain insights into their liquid-state organization, how they solvate different compounds, and what molecular factors determine their properties. The identification of certain ionic liquids as self-organized phases, with aggregated nonpolar and charged domains, provides a new way to interpret the solvation and structure of their mixtures. Many advances are the result of a successful interplay between experiment and modeling, possible in this field where none of the two methodologies had a previous advance. PMID:17661440

  1. Molecular dynamics simulation of imidazolium-based ionic liquids. I. Dynamics and diffusion coefficient

    NASA Astrophysics Data System (ADS)

    Kowsari, M. H.; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

    2008-12-01

    Molecular dynamics simulations are used to study the dynamics and transport properties of 12 room-temperature ionic liquids of the 1-alkyl-3-methylimidazolium [amim]+ (alkyl=methyl, ethyl, propyl, and butyl) family with PF6-, NO3-, and Cl- counterions. The explicit atom transferable force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] is used in the simulations. In this first part, the dynamics of the ionic liquids are characterized by studying the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for the centers of mass of the ions at 400 K. Trajectory averaging was employed to evaluate the diffusion coefficients at two temperatures from the linear slope of MSD(t) functions in the range of 150-300 ps and from the integration of the VACF(t) functions at 400 K. Detailed comparisons are made between the diffusion results from the MSD and VACF methods. The diffusion coefficients from the integration of the VACFs are closer to experimental values than the diffusion coefficients calculated from the slope of MSDs. Both methods can show good agreement with experiment in predicting relative trends in the diffusion coefficients and determining the role of the cation and anion structures on the dynamical behavior of this family of ionic liquids. The MSD and self-diffusion of relatively heavier imidazolium cations are larger than those of the lighter anions from the Einstein results, except for the case of [bmim][Cl]. The cationic transference number generally decreases with temperature, in good agreement with experiments. For the same anion, the cationic transference numbers decrease with increasing length of the alkyl chain, and for the same cation, the trends in the cationic transference numbers are [NO3]-<[Cl]-<[PF6]-. The trends in the diffusion coefficient in the series of cations with identical anions are [emim]+>[pmim]+>[bmim]+ and those for anions with identical cations are [NO3]->[PF6]->[Cl]-. The [dmim]+ has a relatively low diffusion coefficient due to its symmetric structure and good packing in the liquid phase. The major factor for determining the magnitude of the self-diffusion is the geometric shape of the anion of the ionic liquid. Other important factors are the ion size and the charge delocalization in the anion.

  2. Room temperature molten salt electrolytes for photoelectrochemical applications

    SciTech Connect

    Rajeshwar, K.; DuBow, J.; Singh, P.

    1982-08-01

    Mixtures of aluminum chloride (AlCl/sub 3/) with triethylammonium chloride 1,6-ethyl lutidinium bromide (EtluBr), tert-butyl pyridinium bromide (BPBr), and dialkyl imidazolium chloride (R/sub 2/ImCl), in certain molar ratios yielded ionic liquids at room temperature which were studied with respect to their applicability as electrolytes in photoelectrochemical (PEC) cells. Background voltammograms were obtained for these electrolytes on carbon and n-GaAs electrodes. The anodic stability limit was found to be enhanced on n-GaAs relative to carbon in all cases. The cathodic decomposition potential of the electrolyte showed a smaller positive shift on n-GaAs with the exception of the 3:1 AlCl/sub 3/ BPBr electrolyte. The difference in electrolyte stability behavior on carbon and n-GaAs is interpreted in terms of carrier density effects. Cyclic voltammograms were compared on carbon in the various electrolytes for a model redox system comprising the ferrocene/ferricenium couple. The separation of the cathodic and anodic waves in all the cases was consistent with a quasi-reversible redox behavior--the most sluggish electron transfer being observed in the case of the 3:1 AlCl/sub 3/-BpBr electrolyte. Capacitance-voltage measurements were made on n-GaAs electrodes in contact with the various electrolytes. Flatband-potentials (V /SUB fb/) were deduced from these data using Mott-Schottky plots. The implications of this result for PEC applications and the role of specific ion adsorption of electrolyte species on the electrostatic aspects of the n-GaAs/molten salt electrolyte-interface are discussed with the aid of energy band diagrams.

  3. Anionic structure-dependent photoelectrochemical responses of dye-sensitized solar cells based on a binary ionic liquid electrolyte.

    PubMed

    Hao, Feng; Lin, Hong; Liu, Yizhu; Li, Jianbao

    2011-04-14

    Room temperature ionic liquids (RTILs) have been used as electrolytes to investigate the anionic structure dependence of the photoelectrochemical responses of dye-sensitized solar cells (DSCs). A series of RTILs with a fixed cation structure coupling with various anion structures are employed, in which 1-methyl-3-propylimidazolium iodide (PMII) and I(2) are dissolved as redox couples. It is found that both the diffusivity of the electrolyte and the photovoltaic performance of the device show a strong dependence on the fluidity of the ionic liquids, which is primarily altered by the anion structure. Further insights into the structure-dependent physical properties of the employed RTILs are discussed in terms of the reported van der Waals radius, the atomic charge distribution over the anion backbones, the interaction energy of the anion and cation, together with the existence of ion-pairs and ion aggregates. Particularly, both the short-circuit photocurrent and open-circuit voltage exhibit obvious fluidity dependence. Electrochemical impedance and intensity-modulated photovoltage/photocurrent spectroscopy analysis further reveal that increasing the fluidity of the ionic liquid electrolytes could significantly decrease the diffusion resistance of I(3)(-) in the electrolyte, and retard the charge recombination between the injected electrons with triiodide in the high-viscous electrolyte, thus improving the electron diffusion length in the device, as well as the photovoltaic response. However, the variation of the electron diffusion coefficients is trivial primarily due to the effective charge screening of the high cation concentration. PMID:21387030

  4. Nanocomposite semi-solid redox ionic liquid electrolytes with enhanced charge-transport capabilities for dye-sensitized solar cells.

    PubMed

    Rutkowska, Iwona A; Marszalek, Magdalena; Orlowska, Justyna; Ozimek, Weronika; Zakeeruddin, Shaik M; Kulesza, Pawel J; Grätzel, Michael

    2015-08-10

    The ability of Pt nanostructures to induce the splitting of the II bond in iodine (triiodide) molecules is explored here to enhance electron transfer in the iodine/iodide redox couple. Following the dispersal of Pt nanoparticles at 2 % (weight) level, charge transport was accelerated in triiodide/iodide-containing 1,3-dialkylimidazolium room-temperature ionic liquid. If both Pt nanoparticles and multi-walled carbon nanotubes were introduced into the ionic-liquid-based system, a solid-type (nonfluid) electrolyte was obtained. By using solid-state voltammetric (both sandwich-type and microelectrode-based) methodology, the apparent diffusion coefficients for charge transport increased to approximately 1×10(-6)  cm(2)  s(-1) upon the incorporation of the carbon-nanotube-supported iodine-modified Pt nanostructures. A dye-sensitized solar cell comprising TiO2 covered with a heteroleptic Ru(II) -type sensitizer (dye) and the semisolid triiodide/iodide ionic liquid electrolyte admixed with carbon-nanotube-supported Pt nanostructures yielded somewhat higher power conversion efficiencies (up to 7.9 % under standard reporting conditions) than those of the analogous Pt-free system. PMID:26119519

  5. Local coordination and dynamics of a protic ammonium based ionic liquid immobilized in nano-porous silica micro-particles probed by Raman and NMR spectroscopy.

    PubMed

    Garaga, Mounesha N; Persson, Michael; Yaghini, Negin; Martinelli, Anna

    2016-03-01

    Room temperature ionic liquids confined in a solid material, for example, nano-porous silica, are particularly propitious for energy related applications. The aim of this study is to probe the molecular interactions established between the protic ionic liquid diethylmethylammonium methanesulfonate (DEMA-OMs) and silica, where the latter consists of nano-porous micro-particles with pores in the size range of 10 nm. The changes in the local coordination and transport properties induced by the nano-confinement of the ionic liquid are investigated by a combination of Raman and solid-state NMR spectroscopy. In particular, one-dimensional (1D) (1)H and (29)Si and two-dimensional (2D) (29)Si{(1)H} HETOCR solid-state NMR are combined to identify the sites of interaction at the silica-ionic liquid interface. Pulsed field gradient (PFG) NMR experiments are performed to estimate the self-diffusion of both bulk and nano-confined DEMA-OMs. Complementary information on the overall coordination and interaction scheme is achieved by Raman spectroscopy. All these advanced experimental techniques are revealed to be crucial to differentiate between ionic liquid molecules residing in the inter- or intra-particle domains. PMID:26838120

  6. Interaction of Ionic Liquids with a Lipid Bilayer: A Biophysical Study of Ionic Liquid Cytotoxicity.

    PubMed

    Jing, Benxin; Lan, Nan; Qiu, Jie; Zhu, Yingxi

    2016-03-17

    Ionic liquids (ILs) have been widely considered and used as "green solvents" for more than two decades. However, their ecotoxicity results have contradicted this view, as ILs, particularly hydrophobic ones, are reported to exhibit high toxicity. Yet the origin of their toxicology remains unclear. In this work, we have investigated the interaction of amphiphilic ILs with a lipid bilayer as a model cell membrane to understand their cytotoxicity at a molecular level. By employing fluorescence imaging and light and X-ray scattering techniques, we have found that amphiphilic ILs could disrupt the lipid bilayer by IL insertion, end-capping the hydrophobic edge of the lipid bilayer, and eventually disintegrating the lipid bilayer at high IL concentration. The insertion of ILs to cause the swelling of the lipid bilayer shows strong dependence on the hydrophobicity of IL cationic alky chain and anions and is strongly correlated with the reported IL cytotoxicity. PMID:26910537

  7. Determining Camera Gain in Room Temperature Cameras

    SciTech Connect

    Joshua Cogliati

    2010-12-01

    James R. Janesick provides a method for determining the amplification of a CCD or CMOS camera when only access to the raw images is provided. However, the equation that is provided ignores the contribution of dark current. For CCD or CMOS cameras that are cooled well below room temperature, this is not a problem, however, the technique needs adjustment for use with room temperature cameras. This article describes the adjustment made to the equation, and a test of this method.

  8. Ionic Liquid-Modified Thermosets and Their Nanocomposites: Dispersion, Exfoliation, Degradation, and Cure

    NASA Astrophysics Data System (ADS)

    Throckmorton, James A.

    This dissertation explores the application of a room temperature ionic liquid (RTIL) to problems in the chemistry, processing, and modification of thermosetting polymers. In particular, the solution properties and reaction chemistry of 1-ethyl-3-methyl imidazolium dicyanamide (EMIM-DCN) are applied to problems of nanoparticle dispersion and processing, graphite exfoliation, cyanate ester (CE) cure, and the environmental degradation of CEs. Nanoparticle Dispersion: Nanocomposite processing can be simplified by using the same compound as both a nanoparticle solvent and an initiator for polymerization. This dual-function molecule can be designed both for solvent potential and reaction chemistry. EMIM-DCN, previously shown by our lab to act as an epoxy initiator, is used in the synthesis of silica and acid expanded graphite composites. These composites are then characterized for particle dispersion and physical properties. Individual particle dispersion of silica nanocomposites is shown, and silica nanocomposites at low loading show individual particle dispersion and improved modulus and fracture toughness. GNP nanocomposites show a 70% increase in modulus along with a 10-order of magnitude increase in electrical conductivity at 6.5 vol%, and an electrical percolation threshold of 1.7 vol%. Direct Graphite Exfoliation By Laminar Shear: This work presents a laminar-shear alternative to chemical processing and chaotic flow-fields for the direct exfoliation of graphite and the single-pot preparation of nanocomposites. Additionally, we develop the theory of laminar flow through a 3-roll mill, and apply that theory to the latest developments in the theory of graphite interlayer shear. The resulting nanocomposite shows low electrical percolation (0.5 vol%) and low thickness (1-3 layer) graphite/graphene flakes. Additionally, the effect of processing conditions by rheometry and comparison with solvent-free conditions reveal the interactions between processing and matrix properties and provide insight into the theory of the chemical and physical exfoliation of graphite crystals and the resulting polymer matrix dispersion. Cyanate Ester Cure: Dicyanamide-containing ionic liquids decrease the cure temperature of bi- and tri-functional CEs. During the cure reaction, the dicyanamide anion completely reacts and is incorporated into the triazine network. The cure effect was found in many dicyanamide-containing ionic liquids with diverse cations. This invention creates a novel, ionic thermoset polymer. The dicyanamide initiator provides an alternative to metal and hydroxyl catalysts (which have been shown to accelerate degradation and possess human and environmental toxicity). Additionally, the ionic character of the new polymer, rare among thermosets, lends itself to future research and novel applications. RTIL initiation also paves the way to new CE technologies, including RTIL-CE nanocomposites, prepared by graphite exfoliation and nanocomposite dispersion techniques developed herin.

  9. Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy.

    PubMed

    Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil

    2016-04-01

    Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy. PMID:26864750

  10. Physicochemical properties and toxicities of hydrophobicpiperidinium and pyrrolidinium ionic liquids

    SciTech Connect

    Salminen, Justin; Papaiconomou, Nicolas; Kumar, R. Anand; Lee,Jong-Min; Kerr, John; Newman, John; Prausnitz, John M.

    2007-06-25

    Some properties are reported for hydrophobic ionic liquids (IL) containing 1-methyl-1-propyl pyrrolidinium [MPPyrro]{sup +}, 1-methyl-1-butyl pyrrolidinium [MBPyrro]{sup +}, 1-methyl-1-propyl piperidinium [MPPip]{sup +}, 1-methyl-1-butyl piperidinium [MBPip]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPyrro]{sup +} and 1-methyl-1-octylpiperidinium [MOPip]{sup +} cations. These liquids provide new alternatives to pyridinium and imidazolium ILs. High thermal stability of an ionic liquid increases safety in applications like rechargeable lithium-ion batteries and other electrochemical devices. Thermal properties, ionic conductivities, viscosities, and mutual solubilities with water are reported. In addition, toxicities of selected ionic liquids have been measured using a human cancer cell-line. The ILs studied here are sparingly soluble in water but hygroscopic. We show some structure-property relationships that may help to design green solvents for specific applications. While ionic liquids are claimed to be environmentally-benign solvents, as yet few data have been published to support these claims.

  11. Unimolecular Solvolyses in Ionic Liquid: Alcohol Dual Solvent Systems.

    PubMed

    Kochly, Elizabeth D; Lemon, Nicole Jean; Deh-Lee, Anne Marie

    2016-01-01

    A study was undertaken of the solvolysis of pivaloyl triflate in a variety of ionic liquid:alcohol solvent mixtures. The solvolysis is a kΔ process (i.e., a process in which ionization occurs with rearrangement), and the resulting rearranged carbocation intermediate reacts with the alcohol cosolvent via two competing pathways: nucleophilic attack or elimination of a proton. Five different ionic liquids and three different alcohol cosolvents were investigated to give a total of fifteen dual solvent systems. ¹H-NMR analysis was used to determine relative amounts of elimination and substitution products. It was found, not surprisingly, that increasing the bulkiness of alcohol cosolvent led to increased elimination product. The change in the amount of elimination product with increasing ionic liquid concentration, however, varied greatly between ionic liquids. These differences correlate strongly, though not completely, to the Kamlet-Taft solvatochromic parameters of the hydrogen bond donating and accepting ability of the solvent systems. An additional factor playing into these differences is the bulkiness of the ionic liquid anion. PMID:26751434

  12. Recyclability of an ionic liquid for biomass pretreatment.

    PubMed

    Weerachanchai, Piyarat; Lee, Jong-Min

    2014-10-01

    This study investigated the possibility of reusing an ionic liquid for the pretreatment of biomass. The effects of lignin and water content in a pretreatment solvent on pretreatment products were examined, along with the recyclability of an ionic liquid for pretreatment. It was discovered that the presence of lignin and water within a pretreatment solvent resulted in a far less effective pretreatment process. 1-Ethyl-3-methylimidazolium acetate/ethanolamine (60/40 vol%) presents more promising properties than EMIM-AC, providing a small decrease in sugar conversion and also a small increase of lignin deposition with an increasing lignin amount in the pretreatment solvent. Deteriorations of the ionic liquid were observed from considerably low sugar conversions and lignin extraction after using the 5th and 7th batch, respectively. Furthermore, the changes of ionic liquid properties and lignin accumulation in ionic liquid were determined by analyzing their thermal decomposition behavior (TGA) and chemical functional groups (FTIR and (1)H NMR). PMID:25063976

  13. Task-specific ionic liquid for solubilizing metal oxides.

    PubMed

    Nockemann, Peter; Thijs, Ben; Pittois, Stijn; Thoen, Jan; Glorieux, Christ; Van Hecke, Kristof; Van Meervelt, Luc; Kirchner, Barbara; Binnemans, Koen

    2006-10-26

    Protonated betaine bis(trifluoromethylsulfonyl)imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium(II) oxide, mercury(II) oxide, nickel(II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese(II) oxide, and silver(I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous sol