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Sample records for supported ionic liquids

  1. 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

  2. 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.

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

    PubMed

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

    2014-01-01

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

  4. Ionic liquids in refinery desulfurization: comparison between biphasic and supported ionic liquid phase suspension processes.

    PubMed

    Kuhlmann, Esther; Haumann, Marco; Jess, Andreas; Seeberger, Andreas; Wasserscheid, Peter

    2009-01-01

    The desulfurization of fuel compounds in the presence of ionic liquids is reported. For this purpose, the desulfurization efficiency of a variety of imidazolium phosphate ionic liquids has been tested. Dibenzothiophene/dodecane and butylmercaptan/decane mixtures were used as model systems. Single-stage extractions reduced the sulfur content from 500 ppm to 200 ppm. In multistage extractions the sulfur content could be lowered to less than 10 ppm within seven stages. Regeneration of the ionic liquid was achieved by distillation or re-extraction procedures. Supported ionic liquid phase (SILP) materials, obtained by dispersing the ionic liquid as a thin film on highly porous silica, exhibited a significantly higher extraction performance owing to their larger surface areas, reducing the sulfur content to less than 100 ppm in one stage. Multistage extraction with these SILP materials reduced the sulfur level to 50 ppm in the second stage. The SILP technology offers very efficient utilization of ionic liquids and circumvents mass transport limitations because of the small film thickness and large surface area, and allows application of the simple packed-bed column extraction technique. PMID:19798713

  5. 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

  6. 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.

  7. Failure Mechanisms of Hollow Fiber Supported Ionic Liquid Membranes.

    PubMed

    Zeh, Matthew; Wickramanayake, Shan; Hopkinson, David

    2016-01-01

    Hollow fiber supported ionic liquid membranes (SILMs) were tested using the bubble point method to investigate potential failure modes, including the maximum transmembrane pressure before loss of the ionic liquid from the support. Porous hollow fiber supports were fabricated with different pore morphologies using Matrimid(®) and Torlon(®) as the polymeric material and 1-hexyl-3-methylimidalzolium bis(trifluoromethylsulfonyl)imide ([C₆mim][Tf₂N]) as the ionic liquid (IL) component. Hollow fiber SILMs were tested for their maximum pressure before failure, with pressure applied either from the bore side or shell side. It was found that the membranes exhibited one or more of three different modes of failure when pressurized: liquid loss (occurring at the bubble point), rupture, and collapse. PMID:27023620

  8. Failure Mechanisms of Hollow Fiber Supported Ionic Liquid Membranes

    PubMed Central

    Zeh, Matthew; Wickramanayake, Shan; Hopkinson, David

    2016-01-01

    Hollow fiber supported ionic liquid membranes (SILMs) were tested using the bubble point method to investigate potential failure modes, including the maximum transmembrane pressure before loss of the ionic liquid from the support. Porous hollow fiber supports were fabricated with different pore morphologies using Matrimid® and Torlon® as the polymeric material and 1-hexyl-3-methylimidalzolium bis(trifluoromethylsulfonyl)imide ([C6mim][Tf2N]) as the ionic liquid (IL) component. Hollow fiber SILMs were tested for their maximum pressure before failure, with pressure applied either from the bore side or shell side. It was found that the membranes exhibited one or more of three different modes of failure when pressurized: liquid loss (occurring at the bubble point), rupture, and collapse. PMID:27023620

  9. Fabrication of fiber supported ionic liquids and methods of use

    SciTech Connect

    Luebke, David R; Wickramanayake, Shan

    2013-02-26

    One or more embodiments relates to the production of a fabricated fiber having an asymmetric polymer network and having an immobilized liquid such as an ionic liquid within the pores of the polymer network. The process produces the fabricated fiber in a dry-wet spinning process using a homogenous dope solution, providing significant advantage over current fabrication methods for liquid-supporting polymers. The fabricated fibers may be effectively utilized for the separation of a chemical species from a mixture based on the selection of the polymer, the liquid, and the solvent utilized in the dope.

  10. Liquid-Mercury-Supported Langmuir Films of Ionic Liquids: Isotherms, Structure, and Time Evolution.

    PubMed

    Elfassy, Eitan; Mastai, Yitzhak; Pontoni, Diego; Deutsch, Moshe

    2016-04-01

    Ionic liquids have been intensively developed for the last few decades and are now used in a wide range of applications, from electrochemistry to catalysis and nanotechnology. Many of these applications involve ionic liquid interfaces with other liquids and solids, the subnanometric experimental study of which is highly demanding, and has been little studied to date. We present here a study of mercury-supported Langmuir films of imidazolium-based ionic liquids by surface tensiometry and X-ray reflectivity. The charge-delocalized ionic liquids studied here exhibit no 2D lateral order but show diffuse surface-normal electron density profiles exhibiting gradual mercury penetration into the ionic liquid film, and surface-normal structure evolution over a period of hours. The effect of increasing the nonpolar alkyl chain length was also investigated. The results obtained provide insights into the interactions between these ionic liquids and liquid mercury and about the time evolution of the structure and composition of their interface. PMID:26963651

  11. High Temperature Separation of Carbon Dioxide/Hydrogen Mixtures Using Facilitated Supported Ionic Liquid Membranes

    SciTech Connect

    Myers, C.R.; Pennline, H.W.; Luebke, D.R.; Ilconich, J.B.; Dixon, J.K.; Maginn, E.J.; Brennecke, J.F.

    2008-09-01

    Efficiently separating CO2 from H2 is one of the key steps in the environmentally responsible uses of fossil fuel for energy production. A wide variety of resources, including petroleum coke, coal, and even biomass, can be gasified to produce syngas (a mixture of COand H2). This gas stream can be further reacted with water to produce CO2 and more H2. Once separated, the CO2 can be stored in a variety of geological formations or sequestered by other means. The H2 can be combusted to operate a turbine, producing electricity, or used to power hydrogen fuel cells. In both cases, onlywater is produced as waste. An amine functionalized ionic liquid encapsulated in a supported ionic liquid membrane (SILM) can separate CO2 from H2 with a higher permeability and selectivity than any known membrane system. This separation is accomplished at elevated temperatures using facilitated transport supported ionic liquid membranes.

  12. Supported absorption of CO2 by tetrabutylphosphonium amino acid ionic liquids.

    PubMed

    Zhang, Jianmin; Zhang, Suojiang; Dong, Kun; Zhang, Yanqiang; Shen, Youqing; Lv, Xingmei

    2006-05-15

    A new type of "task specific ionic liquid", tetrabutylphosphonium amino acid [P(C4)4][AA], was synthesized by the reaction of tetrabutylphosphonium hydroxide [P(C4)4][OH] with amino acids, including glycine, L-alanine, L-beta-alanine, L-serine, and L-lysine. The liquids produced were characterized by NMR, IR spectroscopies, and elemental analysis, and their thermal decomposition temperature, glass transition temperature, electrical conductivity, density, and viscosity were recorded in detail. The [P(C4)4][AA] supported on porous silica gel effected fast and reversible CO2 absorption when compared with bubbling CO2 into the bulk of the ionic liquid. No changes in absorption capacity and kinetics were found after four cycles of absorption/desorption. The CO2 absorption capacity at equilibrium was 50 mol % of the ionic liquids. In the presence of water (1 wt %), the ionic liquids could absorb equimolar amounts of CO2. The CO2 absorption mechanisms of the ionic liquids with and without water were different. PMID:16528787

  13. 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.

  14. Supported ionic liquid membranes for removal of dioxins from high-temperature vapor streams.

    PubMed

    Kulkarni, Prashant S; Neves, Luisa A; Coelhoso, Isabel M; Afonso, Carlos A M; Crespo, João G

    2012-01-01

    Dioxins and dioxin-like chemicals are predominantly produced by thermal processes such as incineration and combustion at concentrations in the range of 10-100 ng of I-TEQ/kg (I-TEQ = international toxic equivalents). In this work, a new approach for the removal of dioxins from high-temperature vapor streams using facilitated supported ionic liquid membranes (SILMs) is proposed. The use of ceramic membranes containing specific ionic liquids, with extremely low volatility, for dioxin removal from incineration sources is proposed owing to their stability at very high temperatures. Supported liquid membranes were prepared by successfully immobilizing the ionic liquids tri-C(8)-C(10)-alkylmethylammonium dicyanamide ([Aliquat][DCA]) and 1-n-octyl-3-methylimidazolium dicyanamide ([Omim][DCA]) inside the porous structure of ceramic membranes. The porous inorganic membranes tested were made of titanium oxide (TiO(2)), with a nominal pore size of 30 nm, and aluminum oxide (Al(2)O(3)), with a nominal pore size of 100 nm. The ionic liquids were characterized, and the membrane performance was assessed for the removal of dioxins. Different materials (membrane pore size, type of ionic liquid, and dioxin) and different operating conditions (temperature and flow rate) were tested to evaluate the efficiency of SILMs for dioxin removal. All membranes prepared were stable at temperatures up to 200 °C. Experiments with model incineration gas were also carried out, and the results obtained validate the potential of using ceramic membranes with immobilized ionic liquids for the removal of dioxins from high-temperature vapor sources. PMID:22087544

  15. Carbon Dioxide Selective Supported Ionic Liquid Membranes: The Effect of Contaminants

    SciTech Connect

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

    2008-04-01

    The integrated gasification combined cycle (IGCC) is widely viewed as a promising technology for the large scale production of energy in a carbon constrained world. These cycles, which include gasification, contaminant removal, water-gas shift, CO2 capture and compression, and combustion of the reduced-carbon fuel gas in a turbine, often have significant efficiency advantages over conventional combustion technologies. A CO2 selective membrane capable of maintaining performance at conditions approaching those of low temperature water-gas shift (260oC) could facilitate the production of carbon-neutral energy by simultaneously driving the shift reaction to completion and concentrating CO2 for sequestration. Supported ionic liquid membranes (SILMs) have been previously evaluated for this application and determined to be physically and chemically stable to temperatures in excess of 300oC. These membranes were based on ionic liquids which interacted physically with CO2 and diminished considerably in selectivity at higher temperatures. To alleviate this problem, the original ionic liquids were replaced with ionic liquids able to form chemical complexes with CO2. These complexing ionic liquid membranes have a local maximum in selectivity which is observed at increasing temperatures for more stable complexes. Efforts are currently underway to develop ionic liquids with selectivity maxima at temperatures greater than 75oC, the best result to date, but other practical concerns must also be addressed if the membrane is to be realistically expected to function under water-gas shift conditions. A CO2 selective membrane must function not only at high temperature, but also in the presence of all the reactants and contaminants likely to be present in coal-derived fuel gas, including water, CO, and H2S. A study has been undertaken which examines the effects of each of these gases on both complexing and physically interacting supported liquid membranes. In a joint project

  16. Ionic liquid based hollow fiber supported liquid phase microextraction of ultraviolet filters.

    PubMed

    Ge, Dandan; Lee, Hian Kee

    2012-03-16

    Hollow fiber protected liquid phase microextraction using an ionic liquid as supported phase and acceptor phase (IL-HF-LPME) is proposed for the determination of four ultraviolet (UV) filters (benzophenone, 3-(4-methylbenzylidene)-camphor, 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone) in water samples for the first time. In the present study, four different ILs 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate) [HMIM][FAP], 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate [BMPL][FAP], 1-butyl-3-methylimidazolium phosphate ([BMIM][PO(4)]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) were evaluated as extraction solvent. Only [HMIM][FAP] showed high chemical affinity to the analytes which permits a selective isolation of the UV filters from the sample matrix, allowing also their preconcentration. IL-HF-LPME and high performance liquid chromatography provides repeatability from 1.1% to 8.2% and limits of detection between 0.3 and 0.5 ng/ml. Real water samples spiked with the analytes extracted were analyzed, and yielded relative recoveries ranging from 82.6% to 105.9%. PMID:22307149

  17. 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.

  18. 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

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

    PubMed

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

    2012-08-16

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

  20. Life Support Catalyst Regeneration Using Ionic Liquids and In Situ Resources

    NASA Technical Reports Server (NTRS)

    Abney, Morgan B.; Karr, Laurel J.; Paley, Mark S.; Donovan, David N.; Kramer, Teersa J.

    2016-01-01

    Oxygen recovery from metabolic carbon dioxide is an enabling capability for long-duration manned space flight. Complete recovery of oxygen (100%) involves the production of solid carbon. Catalytic approaches for this purpose, such as Bosch technology, have been limited in trade analyses due in part to the mass penalty for high catalyst resupply caused by carbon fouling of the iron or nickel catalyst. In an effort to mitigate this challenge, several technology approaches have been proposed. These approaches have included methods to prolong the life of the catalysts by increasing the total carbon mass loading per mass catalyst, methods for simplified catalyst introduction and removal to limit the resupply container mass, methods of using in situ resources, and methods to regenerate catalyst material. Research and development into these methods is ongoing, but only use of in situ resources and/or complete regeneration of catalyst material has the potential to entirely eliminate the need for resupply. The use of ionic liquids provides an opportunity to combine these methods in a technology approach designed to eliminate the need for resupply of oxygen recovery catalyst. Here we describe the results of an initial feasibility study using ionic liquids and in situ resources for life support catalyst regeneration, we discuss the key challenges with the approach, and we propose future efforts to advance the technology.

  1. 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...

  2. Poly(ionic liquid) complex with spontaneous micro-/mesoporosity: template-free synthesis and application as catalyst support.

    PubMed

    Zhao, Qiang; Zhang, Pengfei; Antonietti, Markus; Yuan, Jiayin

    2012-07-25

    A facile, template-free synthetic route is reported toward poly(ionic liquid) complexes (PILCs) which for the first time exhibit stable micro-/mesoporous structure. This is accomplished via in situ ionic complexation between imidazolium-based PILs and poly(acrylic acid) in various alkaline organic solvents. The PILC can be highly loaded with copper salts and can be used as a catalytic support for effective aerobic oxidation of activated hydrocarbons under mild conditions. PMID:22780888

  3. Interaction of an ionic liquid with a supported phospholipid bilayer is lipid-dependent

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Liquid salts, commonly called ionic liquids, are used as solvents to conduct transformation of vegetable oils into new products. These reactions are often catalyzed via immobilized enzymes. However, some enzymes were found to lose activity and are in need of some protection. Phospholipid bilayers...

  4. The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

    PubMed Central

    Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Luísa A.; Vorotyntsev, Ilya V.

    2015-01-01

    Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S. PMID:26729177

  5. 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

  6. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin

    2011-11-01

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

  7. 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.

  8. Electroplating Using Ionic Liquids

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  9. An Efficient, Versatile, and Safe Access to Supported Metallic Nanoparticles on Porous Silicon with Ionic Liquids.

    PubMed

    Darwich, Walid; Haumesser, Paul-Henri; Santini, Catherine C; Gaillard, Frédéric

    2016-01-01

    The metallization of porous silicon (PSi) is generally realized through physical vapor deposition (PVD) or electrochemical processes using aqueous solutions. The former uses a strong vacuum and does not allow for a conformal deposition into the pores. In the latter, the water used as solvent causes oxidation of the silicon during the reduction of the salt precursors. Moreover, as PSi is hydrophobic, the metal penetration into the pores is restricted to the near-surface region. Using a solution of organometallic (OM) precursors in ionic liquid (IL), we have developed an easy and efficient way to fully metallize the pores throughout the several-µm-thick porous Si. This process affords supported metallic nanoparticles characterized by a narrow size distribution. This process is demonstrated for different metals (Pt, Pd, Cu, and Ru) and can probably be extended to other metals. Moreover, as no reducing agent is necessary (the decomposition in an argon atmosphere at 50 °C is fostered by surface silicon hydride groups borne by PSi), the safety and the cost of the process are improved. PMID:27271608

  10. Carbon-supported ionic liquids as innovative adsorbents for CO₂ separation from synthetic flue-gas.

    PubMed

    Erto, Alessandro; Silvestre-Albero, Ana; Silvestre-Albero, Joaquín; Rodríguez-Reinoso, Francisco; Balsamo, Marco; Lancia, Amedeo; Montagnaro, Fabio

    2015-06-15

    Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization. PMID:25710387

  11. An Efficient, Versatile, and Safe Access to Supported Metallic Nanoparticles on Porous Silicon with Ionic Liquids

    PubMed Central

    Darwich, Walid; Haumesser, Paul-Henri; Santini, Catherine C.; Gaillard, Frédéric

    2016-01-01

    The metallization of porous silicon (PSi) is generally realized through physical vapor deposition (PVD) or electrochemical processes using aqueous solutions. The former uses a strong vacuum and does not allow for a conformal deposition into the pores. In the latter, the water used as solvent causes oxidation of the silicon during the reduction of the salt precursors. Moreover, as PSi is hydrophobic, the metal penetration into the pores is restricted to the near-surface region. Using a solution of organometallic (OM) precursors in ionic liquid (IL), we have developed an easy and efficient way to fully metallize the pores throughout the several-µm-thick porous Si. This process affords supported metallic nanoparticles characterized by a narrow size distribution. This process is demonstrated for different metals (Pt, Pd, Cu, and Ru) and can probably be extended to other metals. Moreover, as no reducing agent is necessary (the decomposition in an argon atmosphere at 50 °C is fostered by surface silicon hydride groups borne by PSi), the safety and the cost of the process are improved. PMID:27271608

  12. 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

  13. Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier.

    PubMed

    Hintermair, Ulrich; Gong, Zenxing; Serbanovic, Ana; Muldoon, Mark J; Santini, Catherine C; Cole-Hamilton, David J

    2010-09-28

    A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph(2)P(3-C(6)H(4)SO(3))] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf(2) (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF(3)SO(2)) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence of compressed CO(2). Statistical experimental design was used to show that the reaction rate is neither much affected by the film thickness (IL loading) nor by the syngas:substrate ratio. However, a factor-dependent interaction between the syngas:substrate ratio and film thickness on the reaction rate was revealed. Increasing the substrate flow led to increased reaction rates but lower overall yields. One of the most important parameters proved to be the phase behaviour of the mobile phase, which was studied by varying the reaction pressure. At low CO(2) pressures or when N(2) was used instead of CO(2) rates were low because of poor gas diffusion to the catalytic sites in the SILP. Furthermore, leaching of IL and Rh was high because the substrate is liquid and the IL had been designed to dissolve in it. As the CO(2) pressure was increased, the reaction rate increased and the IL and Rh leaching were reduced, because an expanded liquid phase developed. Due to its lower viscosity the expanded liquid allows better transport of gases to the catalyst and is a poorer solvent for the IL and the catalyst because of its reduced polarity. Above 100 bar (close to the transition to a single phase at 106 bar), the rate of reaction dropped again with increasing pressure because the flowing phase becomes a better and better solvent for the alkene, reducing its partitioning into the IL film. Under optimised conditions, the catalyst was shown to be stable over at least 40 h of continuous catalysis with a steady state turnover frequency (TOF, mol product (mol Rh)(-1)) of 500 h(-1) at low Rh leaching (0.2 ppm). The selectivity of the

  14. Hollow fiber-supported designer ionic liquid sponges for post-combustion CO2 scrubbing

    SciTech Connect

    Lee, JS; Hillesheim, PC; Huang, DK; Lively, RP; Oh, KH; Dai, S; Koros, WJ

    2012-11-30

    A proof of concept study for a new type of carbon capture system is considered for post-combustion CO2 capture based on porous hollow fiber sorbents with ionic liquids sorbed in the cell walls of the fiber. This study proves that delicate morphological features in the open-celled porous wall can be maintained during the infusion process. Mixtures of task specific ionic liquid (i.e. [BMIM][Tf2N]) and superbase (i.e. DBU) were loaded into polyamide-imide (PAI) fibers by a so-called two-step non-solvent infusion protocol. In the protocol, methanol carries ionic liquids into the pore cell walls of hollow fibers and then hexane carries superbase to create an efficient CO2 sorbent. Our ionic liquid/superbase impregnation technique overcomes a serious increase in mass transfer resistance upon reaction with CO2, thereby allowing its large scale utilization for post-combustion CO2 capture. The investigation on the effect of different pore former additives (different molecular weights of polyvinylpyrrolidone, lithium nitrate, and their mixtures) suggested that a large molecular weight of PVP (M-w; 1300k) including dope composition produces highly interconnected open cell pore structures of PAI hollow fibers. Lastly, a lumen side barrier layer was successfully formed on the bore side of neat PAI fibers by using a mixture of Neoprene (R) with crosslinking agents (TSR-633) via a post-treatment process. The lumen layer will enable heat removal from the fiber sorbents during their application in rapid thermal swing cycling processes. (C) 2012 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2012-01-01

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

  16. Biocatalytic transformations in ionic liquids.

    PubMed

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

    2003-03-01

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

  17. 3-Methylpiperidinium ionic liquids.

    PubMed

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

    2015-04-28

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

  18. Charge transport in confined ionic liquids

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  19. Dissolving Polymers in Ionic Liquids.

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2009-03-01

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

  20. Effects of Silica Nanoparticle Supported Ionic Liquid as Additive on Thermal Reversibility of Human Carbonic Anhydrase II

    PubMed Central

    Fallahbagheri, Azadeh; Saboury, Ali Akbar; Ma'mani, Leila; Taghizadeh, Mohammad; Khodarahmi, Reza; Ranjbar, Samira; Bohlooli, Mousa; Shafiee, Abbas; Foroumadi, Alireza; Sheibani, Nader; Moosavi-Movahedi, Ali Akbar

    2013-01-01

    Silica nanoparticle supported imidazolium ionic liquid [SNImIL] was synthesized and utilized as a biocompatible additive for studying the thermal reversibility of human carbonic anhydrase II (HCA II). For this purpose, we prepared additive by modification of nanoparticles through the grafting of ionic liquids on the surface of nanoparticles (SNImIL). The SNImIL were fully characterized by Fourier Transform Infrared spectroscopy, scanning electron microscopy and thermo gravimetric analysis. The characterization of HCA II was investigated by various techniques including UV–Vis and ANS fluorescence spectrophotometry, differential scanning calorimetry, and docking study. SNImIL induced disaggregation, enhanced protein stability and increased thermal reversibility of HCA II by up to 42% at pH 7.75. PMID:22829053

  1. 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

  2. Wettability by Ionic Liquids.

    PubMed

    Liu, Hongliang; Jiang, Lei

    2016-01-01

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

  3. Polymeric ionic liquid and carbon black composite as a reusable supporting electrolyte: modification of the electrode surface.

    PubMed

    Yoo, Seung Joon; Li, Long-Ji; Zeng, Cheng-Chu; Little, R Daniel

    2015-03-16

    One of the major impediments to using electroorganic synthesis is the need for large amounts of a supporting electrolyte to ensure the passage of charge. Frequently this causes separation and waste problems. To address these issues, a polymeric ionic liquid-Super P carbon black composite has been formulated. The system enables electrolyses to be performed without adding an additional supporting electrolyte, and its efficient recovery and reuse. In addition, the ability of the composite to modify the electrode surface in situ leads to improved kinetics. A practical consequence is that one can decrease catalyst loading without sacrificing efficiency. PMID:25619992

  4. Ultra-hydrophobic ionic liquid 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate supported hollow-fiber membrane liquid-liquid-liquid microextraction of chlorophenols.

    PubMed

    Ge, Dandan; Lee, Hian Kee

    2015-01-01

    An ultra-hydrophobic ionic liquid, 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]) was immobilized in the pores of a polypropylene hollow fiber for liquid-liquid-liquid microextraction (HF-LLLME) of chlorophenols (CPs) (4-chloro-3-methylphenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol). The analytes were first extracted from 10 ml of water sample into the ionic liquid membrane, and then were extracted back into 5 μl of sodium hydroxide aqueous solution in the hollow fiber channel. After extraction, the acceptor solution was directly injected into a high-performance liquid chromatographic system for analysis. Extraction parameters such as extraction time, salt concentration in the sample, the pH of the sample and acceptor phase, and stirring rate during extraction were investigated. The relative standard deviations of the analytes varied from 4 to 6%. Limits of detection of <0.5 ng/ml were obtained for the three analytes. The squared regression coefficients relating to the calibration curve were ≥0.9941. The proposed method was applied to the analysis of CPs in canal water. PMID:25476289

  5. A Monolithic Hybrid Cellulose-2.5-Acetate/Polymer Bioreactor for Biocatalysis under Continuous Liquid-Liquid Conditions Using a Supported Ionic Liquid Phase.

    PubMed

    Sandig, Bernhard; Michalek, Lukas; Vlahovic, Sandra; Antonovici, Mihaela; Hauer, Bernhard; Buchmeiser, Michael R

    2015-10-26

    Mesoporous monolithic hybrid cellulose-2.5-acetate (CA)/polymer supports were prepared under solvent-induced phase separation conditions using cellulose-2.5-acetate microbeads 8-14 μm in diameter, 1,1,1-tris(hydroxymethyl)propane and 4,4'-methylenebis(phenylisocyanate) as monomers as well as THF and n-heptane as porogenic solvents. 4-(Dimethylamino)pyridine and dibutyltin dilaurate (DBTDL), respectively, were used as catalysts. Monolithic hybrid supports were used in transesterification reactions of vinyl butyrate with 1-butanol under continuous, supported ionic liquid-liquid conditions with Candida antarctica lipase B (CALB) and octylmethylimidazolium tetrafluoroborate ([OMIM(+) ][BF4 (-) ]) immobilized within the CA beads inside the polymeric monolithic framework and methyl tert-butyl ether (MTBE) as the continuous phase. The new hybrid bioreactors were successfully used in dimensions up to 2×30 cm (V=94 mL). Under continuous biphasic liquid-liquid conditions a constant conversion up to 96 % was achieved over a period of 18 days, resulting in a productivity of 58 μmol mg(-1) (CALB) min(-1) . This translates into an unprecedented turnover number (TON) of 3.9×10(7) within two weeks, which is much higher than the one obtained under standard biphasic conditions using [OMIM(+) ][BF4 (-) ]/MTBE (TON=2.7×10(6) ). The continuous liquid-liquid setup based on a hybrid reactor presented here is strongly believed to be applicable to many other enzyme-catalyzed reactions. PMID:26493884

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

    SciTech Connect

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

    2015-12-08

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

  7. Designing Supported Ionic Liquids (ILs) within Inorganic Nanosheets for CO₂ Capture Applications.

    PubMed

    Zhou, Yingjie; Liu, Jingjing; Xiao, Min; Meng, Yuezhong; Sun, Luyi

    2016-03-01

    A new methodology was developed for the immobilization of ionic liquids (ILs) on α-zirconium phosphate (ZrP) and montmorillonite (MMT) single-layer nanosheets via a facile coassembly process. The coassembled inorganic nanosheet/1-n-butyl-3-methylimidazolium chloride (BMIMCl) hybrids were systematically characterized. The results showed that the ILs were successfully assembled with ZrP or MMT single-layer nanosheets to form an intercalated structure. The inorganic nanosheet/IL hybrids can serve as efficient CO2 absorbents. The CO2 sorption of BMIMCl could be made up to 21 times more efficient because of the high exposure of the functional groups of BMIMCl in the coassembled hybrids. CO2 was physically absorbed by the hybrids with a slow equilibrium time at lower temperatures, whereas higher temperatures allowed for faster diffusion and chemical absorption of CO2. The best CO2 capture capacities of the hybrids were 0.73 mmol/g at 60 °C for ZrP/BMIMCl and 0.42 mmol/g at 70 °C for MMT/BMIMCl. PMID:26840623

  8. Enzyme catalysis in ionic liquids.

    PubMed

    Kragl, Udo; Eckstein, Marrit; Kaftzik, Nicole

    2002-12-01

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

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. Supported Ionic Liquid Membranes and Ion-Jelly® Membranes with [BMIM][DCA]: Comparison of Its Performance for CO2 Separation

    PubMed Central

    Couto, Ricardo; Neves, Luísa; Simões, Pedro; Coelhoso, Isabel

    2015-01-01

    In this work, a supported ionic liquid membrane (SILM) was prepared by impregnating a PVDF membrane with 1-butyl-3-methylimidazolium dicyanamide ([BMIM][DCA]) ionic liquid. This membrane was tested for its permeability to pure gases (CO2, N2 and O2) and ideal selectivities were calculated. The SILM performance was also compared to that of Ion-Jelly® membranes, a new type of gelled membranes developed recently. It was found that the PVDF membrane presents permeabilities for pure gases similar or lower to those presented by the Ion-Jelly® membranes, but with increased ideal selectivities. This membrane presents also the highest ideal selectivity (73) for the separation of CO2 from N2 when compared with SILMs using the same PVDF support but with different ionic liquids. PMID:25594165

  14. 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

  15. Separation and pre-concentration of glucocorticoids in water samples by ionic liquid supported vortex-assisted synergic microextraction and HPLC determination.

    PubMed

    Qin, Hui; Li, Bi; Liu, Mou Sheng; Yang, Ya Ling

    2013-04-01

    We have developed a synergic microextraction procedure based on ionic liquid for the pre-concentration and determination of glucocorticoids in water samples. Using nonionic surfactant Triton X-100 (TX-100) as synergic reagent, 1-butyl-3-methylimidazolium hexa-fluorophosphate accomplished extraction rapidly without heating in water bath. One key property of ionic liquids that highlights their potential is their wide liquid temperature range. The improved extraction was named as ionic liquid supported vortex-assisted synergic microextraction. Compared with the traditional liquid-liquid extraction and cloud point extraction, ionic liquid supported vortex-assisted synergic microextraction was accomplished in 8 min with considerably high recovery. The proposed method greatly improved the sensitivity of HPLC for the determination of glucocorticoids. The results obtained indicated a good linearity with the correlation coefficient of 0.997 over the range of 0.6-300 ng/mL and high sensitivity with LODs of 4.11, 9.19, and 7.50 ng/mL for hydrocortisone butyrate, beclomethasone dipropionate, and nandrolone phenylpropionate, respectively. The RSD of the method was 1.57-1.81% (n = 6) with enrichment factor of 99.85, and good recovery (≥97.24%). The method was successfully applied to the determination of glucocorticoids in mineral water, water of Dianchi lake, and tap water samples. PMID:23418157

  16. 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.

  17. Highly cis-selective and lead-free hydrogenation of 2-hexyne by a supported Pd catalyst with an ionic-liquid layer.

    PubMed

    Schwab, Frederick; Weidler, Natascha; Lucas, Martin; Claus, Peter

    2014-09-18

    A simple Pd/SiO2 catalyst which was modified with the ionic liquid [BMPL][DCA] gave an excellent yield of 88% towards cis-2-hexene in the stereoselective hydrogenation of 2-hexyne. The catalyst outperforms, even at full conversion, the commonly used lead-poisoned, toxic Lindlar catalyst and supported colloidal-based Pd as well. PMID:25069061

  18. 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...

  19. Experimental investigation of the permeability and selectivity of supported ionic liquid membranes for CO2/He separation at temperatures up to 125° C

    SciTech Connect

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

    2007-07-01

    Supported liquid membranes have been prepared by impregnation of commercial porous polymer films with the ionic liquid 1-n-hexyl-3- methylimidazolium bis(trifluoromethanesulfonyl)imide. The ionic liquid has been characterized, and the membranes have been tested to determine performance in the selective separation of CO2 from He. Experiments were conducted in a constant pressure system, and pure gas permeability/selectivity data are reported. Membranes prepared with polysulfone supports have been found to be stable to 125 °C. The CO2 permeability of the membranes increases from 744 to 1200 barrer as the temperature increases from 37 to 125 °C. The CO2/He selectivity decreased from 8.7 to 3.1 over the same temperature range.

  20. Externally Wetted Ionic Liquid Thruster

    NASA Astrophysics Data System (ADS)

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

    2004-10-01

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

  1. 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.

  2. The hype with ionic liquids as solvents

    NASA Astrophysics Data System (ADS)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

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

  3. 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

  4. 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

  5. Application of ionic liquids in hydrometallurgy.

    PubMed

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

    2014-01-01

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

  6. Retreating behavior of a charged ionic liquid droplet in a dielectric liquid under electric field

    NASA Astrophysics Data System (ADS)

    Ahn, Myung Mo; Im, Do Jin; Kang, In Seok

    2013-11-01

    Ionic liquids show great promise as excellent solvents or catalysts in energy and biological fields due to their unique chemical and physical properties. The ionic liquid droplets in microfluidic systems can also be used as a potential platform for chemical biological reactions. In order to control electrically the ionic liquid droplets in a microfluidic device, the charging characteristics of ionic liquid droplets need to be understood. In this work, the charging characteristics of various ionic liquids are investigated by using the parallel plate electrodes system. Under normal situation, a charged droplet shows bouncing motion between electrodes continuously. However, for some special ionic liquids, interesting retreating behavior of charged ionic liquid droplet has been observed. This retreating behavior of ionic liquid droplet has been analyzed experimentally by the image analysis and the electrometer signal analysis. Based on the hypothesis of charge leakage of the retreating ionic liquid droplets, FT-IR spectroscopy analysis has also been performed. The retreating behavior of ionic liquid droplet is discussed from the intermolecular point of view according to the species of ionic liquids. This research was supported by grant No. 2013R1A1A2011956 funded by the Ministry of Science, ICT and Future Planning (MSIP) and by grant No. 2013R1A1A2010483 funded by the Ministry of Education, Science and Technology (MEST) through the NRF.

  7. 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.

  8. 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.

  9. Enzyme catalysis with small ionic liquid quantities.

    PubMed

    Fischer, Fabian; Mutschler, Julien; Zufferey, Daniel

    2011-04-01

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

  10. 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.

  11. Membrane separation of ionic liquid solutions

    SciTech Connect

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

    2015-09-01

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

  12. Ionic liquid tunes microemulsion curvature.

    PubMed

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

    2009-02-17

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

  13. Quantized friction across ionic liquid thin films.

    PubMed

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

    2013-10-01

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

  14. 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.

  15. Ionic liquid-in-oil microemulsions.

    PubMed

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

    2005-05-25

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

  16. 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.

  17. Thermal boundary conductance of hydrophilic and hydrophobic ionic liquids

    NASA Astrophysics Data System (ADS)

    Oyake, Takafumi; Sakata, Masanori; Yada, Susumu; Shiomi, Junichiro

    2015-03-01

    A solid/liquid interface plays a critical role for understanding mechanisms of biological and physical science. Moreover, carrier density of the surface is dramatically enhanced by electric double layer with ionic liquid, salt in the liquid state. Here, we have measured the thermal boundary conductance (TBC) across an interface of gold thin film and ionic liquid by using time-domain thermoreflectance technique. Following the prior researches, we have identified the TBC of two interfaces. One is gold and hydrophilic ionic liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF4), which is a hydrophilic ionic liquid, and the other is N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI), which is a hydrophobic ionic liquid. We found that the TBC between gold and DEME-TFIS (19 MWm-2K-1) is surprisingly lower than the interface between gold and DEME-BF4 (45 MWm-2K-1). With these data, the importance of the wetting angle and ion concentration for the thermal transport at the solid/ionic liquid interface is discussed. Part of this work is financially supported by Japan Society for the Promotion of Science (JSPS) and Japan Science and Technology Agency. The author is financially supported by JSPS Fellowship.

  18. Ionic liquid incorporating thiosalicylate for metal removal

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  19. One-step synthesis of highly efficient nanocatalysts on the supports with hierarchical pores using porous ionic liquid-water gel.

    PubMed

    Kang, Xinchen; Zhang, Jianling; Shang, Wenting; Wu, Tianbin; Zhang, Peng; Han, Buxing; Wu, Zhonghua; Mo, Guang; Xing, Xueqing

    2014-03-12

    Stable porous ionic liquid-water gel induced by inorganic salts was created for the first time. The porous gel was used to develop a one-step method to synthesize supported metal nanocatalysts. Au/SiO2, Ru/SiO2, Pd/Cu(2-pymo)2 metal-organic framework (Cu-MOF), and Au/polyacrylamide (PAM) were synthesized, in which the supports had hierarchical meso- and macropores, the size of the metal nanocatalysts could be very small (<1 nm), and the size distribution was very narrow even when the metal loading amount was as high as 8 wt %. The catalysts were extremely active, selective, and stable for oxidative esterification of benzyl alcohol to methyl benzoate, benzene hydrogenation to cyclohexane, and oxidation of benzyl alcohol to benzaldehyde because they combined the advantages of the nanocatalysts of small size and hierarchical porosity of the supports. In addition, this method is very simple. PMID:24575937

  20. Homopolymer Dissolution in a Hydrophilic Ionic Liquid

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2010-03-01

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

  1. Fast Ignition and Sustained Combustion of Ionic Liquids

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

  2. 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

  3. 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.

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

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

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

  5. 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.

  6. 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

  7. Ionic liquid lubrication at electrified interfaces

    NASA Astrophysics Data System (ADS)

    Kong, Lingling; Huang, Wei; Wang, Xiaolei

    2016-06-01

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

  8. 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.

  9. Catalytic reactions in ionic liquids.

    PubMed

    Sheldon, R

    2001-12-01

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

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

    PubMed

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

    2012-10-14

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

  11. Phosphonium-based ionic liquids and uses

    SciTech Connect

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

    2014-12-30

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

  12. 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.

  13. 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.

  14. High CO2 solubility, permeability and selectivity in ionic liquids with the tetracyanoborate anion

    SciTech Connect

    Mahurin, SM; Hillesheim, PC; Yeary, JS; Jiang, DE; Dai, S

    2012-01-01

    Five different ionic liquids containing the tetracyanoborate anion were synthesized and evaluated for CO2 separation performance. Measured CO2 solubility values were exceptionally high compared to analogous ionic liquids with different anions and ranged from 0.128 mol L-1 atm(-1) to 0.148 mol L-1 atm(-1). In addition, CO2 permeability and CO2/N-2 selectivity values were measured using a supported ionic liquid membrane architecture and the separations performance of the ionic liquid membranes exceeded the Robeson upper bound. These results establish the distinct potential of ionic liquids with the tetracyanoborate, [B(CN)(4)], anion for the separation of CO2.

  15. 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.

  16. Anomalous Wien Effects in Supercooled Ionic Liquids.

    PubMed

    Patro, L N; Burghaus, O; Roling, B

    2016-05-01

    We have measured conductivity spectra of several supercooled monocationic and dicationic ionic liquids in the nonlinear regime by applying ac electric fields with large amplitudes up to about 180  kV/cm. Thereby, higher harmonic ac currents up to the 7th order were detected. Our results point to the existence of anomalous Wien effects in supercooled ionic liquids. Most ionic liquids studied here exhibit a conductivity-viscosity relation, which is close to the predictions of the Nernst-Einstein and Stokes-Einstein equations, as observed for classical strong electrolytes like KCl. These "strong" ionic liquids show a much stronger nonlinearity of the conductivity than classical strong electrolytes. On the other hand, the conductivity-viscosity relation of the ionic liquid [P_{6,6,6,14}][Cl] points to ion association effects. This "weak" ionic liquid shows a strength of the nonlinear effect, which is comparable to classical weak electrolytes. However, the nonlinearity increases quadratically with the field. We suggest that a theory for explaining these anomalies will have to go beyond the level of Coulomb lattice gas models. PMID:27203333

  17. 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

  18. 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.

  19. Ultrafast dynamics of pyrrolidinium cation ionic liquids.

    PubMed

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

    2005-05-01

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

  20. Ultrafast dynamics of pyrrolidinium cation ionic liquids

    NASA Astrophysics Data System (ADS)

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

    2005-05-01

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

  1. Ionic liquids--an overview.

    PubMed

    Jenkins, Harry Donald Brooke

    2011-01-01

    A virtually unprecedented exponential burst of activity resulted following the publication, in 1998, of an article by Michael Freeman (Freemantle, M. Chemical & Engineering News, 1998, March 30, 32), which speculated on the role and contribution that ionic liquids (ILs) might make in the future on the development of clean technology. Up until that time only a handful of researchers were routinely engaged in the study of ILs but frenzied activity followed that continues until the present day. Scientists from all disciplines related to Chemistry have now embarked on studies, including theoreticians who are immersed in the aim of improving the "designer role" so that they can tailor ILs to deliver specified properties. This article, whilst not in any sense attempting to be exhaustive, highlights the main features which characterise ILs, presenting these in a form readily assimilated by newcomers to this area of research. An extensive glossary is featured in this article as well as a chronological list which charts the major areas of development. What follows consists of a number of sections briefly describing the role of lLs as solvents, hypergolic fuels, their use in some electrochemical devices such as solar cells and lithium batteries and their use in polymerisation reactions, followed by a concise summary of some of the other roles that they are capable of playing. The role of empirical, volume-based thermodynamics procedures, as well as large scale computational studies on ILs is also highlighted. These developments which are described are remarkable in that they have been achieved in less than a decade and a half although knowledge of these materials has existed for much longer. PMID:22026149

  2. Ionic liquids behave as dilute electrolyte solutions

    PubMed Central

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

    2013-01-01

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

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. Cr(VI) transport via a supported ionic liquid membrane containing CYPHOS IL101 as carrier: system analysis and optimization through experimental design strategies.

    PubMed

    Rodríguez de San Miguel, Eduardo; Vital, Xóchitl; de Gyves, Josefina

    2014-05-30

    Chromium(VI) transport through a supported liquid membrane (SLM) system containing the commercial ionic liquid CYPHOS IL101 as carrier was studied. A reducing stripping phase was used as a mean to increase recovery and to simultaneously transform Cr(VI) into a less toxic residue for disposal or reuse. General functions which describe the time-depending evolution of the metal fractions in the cell compartments were defined and used in data evaluation. An experimental design strategy, using factorial and central-composite design matrices, was applied to assess the influence of the extractant, NaOH and citrate concentrations in the different phases, while a desirability function scheme allowed the synchronized optimization of depletion and recovery of the analyte. The mechanism for chromium permeation was analyzed and discussed to contribute to the understanding of the transfer process. The influence of metal concentration was evaluated as well. The presence of different interfering ions (Ca(2+), Al(3+), NO3(-), SO4(2-), and Cl(-)) at several Cr(VI): interfering ion ratios was studied through the use of a Plackett and Burman experimental design matrix. Under optimized conditions 90% of recovery was obtained from a feed solution containing 7mgL(-1) of Cr(VI) in 0.01moldm(-3) HCl medium after 5h of pertraction. PMID:24751491

  8. Ionic Liquid Extractions of Soil Organic Matter

    NASA Astrophysics Data System (ADS)

    Patti, Antonio; Macfarlane, Douglas; Clarke, Michael

    2010-05-01

    A large range of ionic liquids with the ability to dissolve different classes of natural biopolymers (e.g. cellulose, lignin, protein) have been reported in the literature. These have the potential to isolate different fractions of soil organic matter, thus yielding novel information that is not available through other extraction procedures. The ionic liquids dimethylammonium dimethylcarbamate (DIMCARB), alkylbenzenesulfonate and 1-butyl-3methylimidazolium chloride (Bmim Cl) can solubilise selected components of soil organic matter. Soil extractions with these materials showed that the organic matter recovered showed chemical properties that were consistent with humic substances. These extracts had a slightly different organic composition than the humic acids extracted using the traditional International Humic Substances Society (IHSS) method. The ionic liquids also solubilised some inorganic matter from the soil. Humic acids recovered with alkali were also partially soluble in the ionic liquids. DIMCARB appeared to chemically interfere with organic extract, increasing the level of nitrogen in the sample. It was concluded that the ionic liquid Bmim Cl may function as a useful solvent for SOM, and may be used to recover organic matter of a different character to that obtained with alkali

  9. Ionic conductivity of imidazole-functionalized liquid crystal mesogens

    NASA Astrophysics Data System (ADS)

    Roddecha, Supacharee; Anthamatten, Mitchell

    2012-02-01

    Imidazole has been investigated as a novel anhydrous proton conducting functional group that could enable higher temperature operation (> 120 ^oC) of polymer electrolyte fuel cells. Its amphoteric behavior can support Grotthuss-like proton transport; however molecular mobility and a high concentration of imidazole groups are needed to achieve high ionic conductivity. Our hypothesis is that liquid crystal ordering, particularly in layered smectic phase, can facilitate formation of 2D proton transport and promote proton conductivity. We have designed and synthesized two imidazole-terminated liquid crystal mesogens, and the ionic conductivities in the liquid crystalline and isotropic states have been measured. Here we report on synthesis and characterization of diacylhydrazine liquid crystals bearing imidazole terminal groups. The proton conductivity of products is compared to pure liquid imidazole and to liquid crystal mesogens without imidazole groups.

  10. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    NASA Astrophysics Data System (ADS)

    Cha, E. H.; Lim, S. A.; Park, J. H.; Kim, D. W.; Macfarlane, D. R.

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N, N-dimethyl- N-propyl- N-butyl ammonium tricyanomethanide (N 1134TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 × 10 -3 S cm -1 at 25 °C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 × 10 -3 S cm -1 at 25 °C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N 1134TCM (2.48 × 10 -3 S cm -1). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N 1134TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species.

  11. Enzyme activity in dialkyl phosphate ionic liquids.

    PubMed

    Thomas, Marie F; Li, Luen-Luen; Handley-Pendleton, Jocelyn M; van der Lelie, Daniel; Dunn, John J; Wishart, James F

    2011-12-01

    The activity of four metagenomic enzymes and an enzyme cloned from the straw mushroom, Volvariella volvacea were studied in the following ionic liquids, 1,3-dimethylimidazolium dimethyl phosphate, [mmim][dmp], 1-ethyl-3-methylimidazolium dimethyl phosphate, [emim][dmp], 1-ethyl-3-methylimidazolium diethyl phosphate, [emim][dep] and 1-ethyl-3-methylimidazolium acetate, [emim][OAc]. Activity was determined by analyzing the hydrolysis of para-nitrobenzene carbohydrate derivatives. In general, the enzymes were most active in the dimethyl phosphate ionic liquids, followed by acetate. Generally speaking, activity decreased sharply for concentrations of [emim][dep] above 10% v/v, while the other ionic liquids showed less impact on activity up to 20% v/v. PMID:22001053

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Structure of room temperature ionic liquids.

    PubMed

    Yethiraj, Arun

    2016-10-19

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

  17. High-Surface-Area CO2 Sponge: High Performance CO2 Scrubbing Based on Hollow Fiber-Supported Designer Ionic Liquid Sponges

    SciTech Connect

    2010-09-01

    IMPACCT Project: The team from ORNL and Georgia Tech is developing a new technology that will act like a sponge, integrating a new, alcohol-based ionic liquid into hollow fibers (magnified image, right) to capture CO2 from the exhaust produced by coal-fired power plants. Ionic liquids, or salts that exist in liquid form, are promising materials for carbon capture and storage, but their tendency to thicken when combined with CO2 limits their efficiency and poses a challenge for their development as a cost-effective alternative to current-generation solutions. Adding alcohol to the mix limits this tendency to thicken in the presence of CO2 but can also make the liquid more likely to evaporate, which would add significantly to the cost of CO2 capture. To solve this problem, ORNL is developing new classes of ionic liquids with high capacity for absorbing CO2. ORNL’s sponge would reduce the cost associated with the energy that would need to be diverted from power plants to capture CO2 and release it for storage.

  18. 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.

  19. Hollow-fiber-supported liquid-phase microextraction using an ionic liquid as the extractant for the pre-concentration of bisphenol A, 17-β-estradiol, estrone and diethylstilbestrol from water samples with HPLC detection.

    PubMed

    Zou, Yanmin; Zhang, Zhen; Shao, Xiaoling; Chen, Yao; Wu, Xiangyang; Yang, Liuqing; Zhu, Jingjing; Zhang, Dongmei

    2014-01-01

    A new method for the determination of four endocrine disrupting compounds (EDCs) (bisphenol A, 17-β-estradiol, estrone and diethylstilbestrol) in water samples has been developed using polypropylene hollow-fiber-supported ionic liquid (IL, 1-Octyl-3-methylimidazolium hexafluorophosphate, [C8MIM][PF6]) microextraction [HF-liquid-phase microextraction (LPME)] combined with high-performance liquid chromatography (HPLC)/UV. This method was used to investigate pollutants in surface water, on the Neijiang River, located at Zhenjiang, Jiangsu Province. Several parameters (sample pH, volume of accepter phase, ionic strength) were investigated. Under the optimum extraction conditions (sample pH, 2.0; volume of extraction solvent, 2.5 μL; ionic strength, 2.57) the proposed method offered: good linearity range, 0.15-100 μg L(-1), with the correlation coefficients (r(2)) of 0.9996, 0.9994, 0.9990 and 0.9984, respectively; low limits of detection, 0.03, 0.05, 0.10, 0.05 μg L(-1) (S/N = 3) for bisphenol A, 17-β-estradiol, estrone and diethylstilbestrol, respectively; good reproducibility (relative standard deviation (RSD), 8.41, 7.61, 9.00, 7.22%, respectively, n = 5); satisfactory recoveries (80.2-107.1%, n = 5); and high enrichment factors, 5,240, 3,693, 2,425 and 2,086, were achieved, for the four chemicals, respectively. Using the proposed HF-LPME, among 15 sampling sites along Neijiang River, bisphenol A, diethylstilbestrol and 17-β-estradiol were detected in some sites, all of which were the near suburban sampling sites. The results indicate that the role of municipal sewage is an important source of EDC contamination. PMID:24622552

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

    SciTech Connect

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

    2012-09-05

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

  1. An ultrasensitive lysozyme chemiluminescence biosensor based on surface molecular imprinting using ionic liquid modified magnetic graphene oxide/β-cyclodextrin as supporting material.

    PubMed

    Duan, Huimin; Wang, Xiaojiao; Wang, Yanhui; Sun, Yuanling; Li, Jianbo; Luo, Chuannan

    2016-04-28

    In this work, ionic liquid modified Fe3O4@dopamine/graphene oxide/β-cyclodextrin (ILs-Fe3O4@DA/GO/β-CD) was used as supporting material to synthesize surface molecularly imprinted polymer (SMIP) which then was introduced into chemiluminescence (CL) to achieve an ultrasensitive and selective biosensor for determination of lysozyme (Lys). ILs and β-CD was applied to provide multiple binding sites to prepare Lys SMIP and Fe3O4@DA was designed to make the product separate easily and prevent the aggregation of GO which could improve absorption capacity for its large specific surface area. The ILs-Fe3O4@DA/GO/β-CD-SMIP showed high adsorption capacity (Q = 101 mg/g) to Lys in the adsorption isotherm assays. The adsorption equilibrium was reached within 10 min for all the concentrations, attributing to the binding sites situated exclusively at the surface, and the adsorption model followed Langmuir isotherm. Under the suitable CL conditions, the proposed biosensor could response Lys linearly in the range of 1.0 × 10(-9)-8.0 × 10(-8) mg/mL with a detection limit of 3.0 × 10(-10) mg/mL. When used in practical samples in determination of Lys, the efficient biosensor exhibited excellent result with the recoveries ranging from 94% to 112%. PMID:27046214

  2. EXPEDITIOUS SYNTHESIS OF IONIC LIQUIDS USING ULTRASOUND AND MICROWAVE IRRADIATION

    EPA Science Inventory

    Environmentally friendlier preparations of ionic liquids have been developed that proceed expeditiously under the influence of microwave or ultrasound irradiation conditions using neat reactants, alkylimidazoles and alkyl halides. A number of useful ionic liquids have been prepar...

  3. 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

  4. 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.

  5. 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

  6. Carbon dioxide in ionic liquid microemulsions.

    PubMed

    Zhang, Jianling; Han, Buxing; Li, Jianshen; Zhao, Yueju; Yang, Guanying

    2011-10-10

    Tailor-made emulsion: a CO(2) -in-ionic-liquid microemulsion was produced for the first time. The CO(2)-swollen micelles are "tunable" because the micellar size can be easily adjusted by changing the pressure of CO(2). The microemulsion has potential applications in materials synthesis, chemical reactions, and extraction. PMID:21898733

  7. 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.

  8. 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...

  9. 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...

  10. Application of Ionic Liquids in Amperometric Gas Sensors.

    PubMed

    Gębicki, Jacek; Kloskowski, Adam; Chrzanowski, Wojciech; Stepnowski, Piotr; Namiesnik, Jacek

    2016-01-01

    This article presents an analysis of available literature data on metrological parameters of the amperometric gas sensors containing ionic liquids as an electrolyte. Four mechanism types of signal generation in amperometric sensors with ionic liquid are described. Moreover, this article describes the influence of selected physico-chemical properties of the ionic liquids on the metrological parameters of these sensors. Some metrological parameters are also compared for amperometric sensors with GDE and SPE electrodes and with ionic liquids for selected analytes. PMID:25830724

  11. 'Liquid litmus': chemosensory pH-responsive photonic ionic liquids.

    PubMed

    Yung, Ka Yi; Schadock-Hewitt, Abby J; Hunter, Neil P; Bright, Frank V; Baker, Gary A

    2011-04-28

    We report on the founding member of a unique class of luminescent ionic liquids integrating a photoacidic anion that responds to the presence of both condensed- and gas-phase basicity; the analytical response is ratiometric in nature, visible to the naked eye, and offers fascinating prospects in smart photofluids, liquid logic gates, electronic noses, and sensory inks. PMID:21399813

  12. Magnesium Battery Electrolytes in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Watkins, Tylan Strike

    A lack of adequate energy storage technologies is arguably the greatest hindrance to a modern sustainable energy infrastructure. Chemical energy storage, in the form of batteries, is an obvious solution to the problem. Unfortunately, today's state of the art battery technologies fail to meet the desired metrics for full scale electric grid and/or electric vehicle role out. Considerable effort from scientists and engineers has gone into the pursuit of battery chemistries theoretically capable of far outperforming leading technologies like Li-ion cells. For instance, an anode of the relatively abundant and cheap metal, magnesium, would boost the specific energy by over 4.6 times that of the current Li-ion anode (LiC6). The work presented here explores the compatibility of magnesium electrolytes in TFSI---based ionic liquids with a Mg anode (TFSI = bis(trifluoromethylsulfonyl)imide). Correlations are made between the Mg2+ speciation conditions in bulk solutions (as determined via Raman spectroscopy) and the corresponding electrochemical behavior of the electrolytes. It was found that by creating specific chelating conditions, with an appropriate Mg salt, the desired electrochemical behavior could be obtained, i.e. reversible electrodeposition and dissolution. Removal of TFSI -- contact ion pairs from the Mg2+ solvation shell was found to be essential for reversible electrodeposition. Ionic liquids with polyethylene glycol chains pendent from a parent pyrrolidinium cation were synthesized and used to create the necessary complexes with Mg 2+, from Mg(BH4)2, so that reversible electrodeposition from a purely ionic liquid medium was achieved. The following document discusses findings from several electrochemical experiments on magnesium electrolytes in ionic liquids. Explanations for the failure of many of these systems to produce reversible Mg electrodeposition are provided. The key characteristics of ionic liquid systems that are capable of achieving reversible Mg

  13. Ionic liquid containing hydroxamate and N-alkyl sulfamate ions

    DOEpatents

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

    2016-03-15

    Embodiments of the invention are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes a cation and an anion selected from hydroxamate and/or N-alkyl sulfamate anions.

  14. Synthesis of electroactive ionic liquids for flow battery applications

    SciTech Connect

    Anderson, Travis Mark; Ingersoll, David; Staiger, Chad; Pratt, Harry

    2015-09-01

    The present disclosure is directed to synthesizing metal ionic liquids with transition metal coordination cations, where such metal ionic liquids can be used in a flow battery. A cation of a metal ionic liquid includes a transition metal and a ligand coordinated to the transition metal.

  15. High CO2 Solubility, Permeability and Selectivity in Ionic Liquids with the Tetracyanoborate Anion

    SciTech Connect

    Mahurin, Shannon Mark; Hillesheim, Patrick C; Yeary, Joshua S; Jiang, Deen; Dai, Sheng

    2012-01-01

    Five different ionic liquids containing the tetracyanoborate anion were synthesized and evaluated for CO2 separation performance. Measured CO2 solubility values were exceptionally high compared to analogous ionic liquids with different anions and ranged from 0.128 mol L-1 atm-1 to 0.148 mol L-1 atm-1. In addition, CO2 permeability and CO2/N2 selectivity values were measured using a supported ionic liquid membrane architecture and the separations performance of the ionic liquid membranes exceeded the Robeson upper bound. These results establish the distinct potential of the tetracyanoborate, [B(CN)4], anion for the separation of CO2.

  16. Correlation of three-liquid-phase equilibria involving ionic liquids.

    PubMed

    Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A

    2016-08-01

    The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results. PMID:27427420

  17. Polymer-supported ionic liquid solid phase extraction for trace inorganic and organic mercury determination in water samples by flow injection-cold vapor atomic absorption spectrometry.

    PubMed

    Escudero, Leticia B; Olsina, Roberto A; Wuilloud, Rodolfo G

    2013-11-15

    A simple and green technique named polymer-supported ionic liquid solid phase extraction (PSIL-SPE) was developed for mercury (Hg) species determination. Inorganic Hg (InHg) species was complexed with chloride ions followed by its introduction into a flow injection on-line system to quantitatively retain the anionic chlorocomplex (HgCl4(2-)) in a column packed with CYPHOS(®) IL 101-impregnated resin. The trapped InHg was then reduced with stannous chloride (SnCl2) and eluted with the same flow of reducing agent followed by cold vapor atomic absorption spectrometry (CV-AAS) detection. Organic mercury species (OrgHg) did not interact with the impregnated resin and were not retained into the column. Total concentration of OrgHg was evaluated by difference between total Hg and InHg concentration. A 95% extraction efficiency was achieved for InHg when the procedure was developed under optimal experimental conditions. The limit of detection obtained for preconcentration of 40 mL of sample was 2.4 ng L(-1) InHg. The relative standard deviation (RSD) was 2.7% (at 1 µg L(-1) InHg and n=10) calculated from the peak height of absorbance signals (Gaussian-shape and reproducible peaks). This work reports the first polymer-supported IL solid phase extraction approach implemented in a flow injection on-line system for determination of Hg species in mineral, tap and river water samples. PMID:24148384

  18. Active chemisorption sites in functionalized ionic liquids for carbon capture.

    PubMed

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

    Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined. PMID:27243042

  19. 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.

  20. Ionic liquids as surfactants in micellar liquid chromatography.

    PubMed

    Flieger, Jolanta; Siwek, Agata; Pizoń, Magdalena; Czajkowska-Żelazko, Anna

    2013-05-01

    This paper is devoted to application of ionic liquids as surfactants in LC of organic compounds, derivatives of 1,4-thiosemicarbazides. According to HPLC requirements the most advantageous conditions such as transparency for ultraviolet light, low CMC, additional inorganic salt additives, and appropriate organic solvent were established. The CMC was determined using conductivity measurements. Suitability of two different stationary phases: RP-C18 and cyanopropyl bonded phase was examined under micellar conditions. Chosen ionic liquid surfactant was compared to common traditional amphiphilic reagent - SDS. Elaborated on chromatographic micellar conditions were tested as a pilot technique for prediction of distribution coefficients of organic analytes in ionic liquid-based aqueous two-phase system. PMID:23609988

  1. 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

  2. Structural and Aggregation Study of Protic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Mattedi, S.; Martin-Pastor, M.; Iglesias, M.

    2011-12-01

    In this work there were studied structural and agreggation aspects of ionic liquids formed by the reaction between ethanolamines with low chain organic acids using NMR techniques. Three ionic liquids composed of pentanoic acid and (mono-, di- and tri-) ethanol amine were studied by 1H, and 13C solution NMR methods. NMR assisted the chemical and quantitative characterization of these three ionic liquids and provided insight in their structural arrangement of their components in the ionic liquid medium. The obtained results could be used to understand the structure and aggregation pattern of these ionic liquids and helps in the development of possible industrial applications.

  3. [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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed

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

    2016-06-14

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

  6. Dynamics of Ion Transport in Ionic Liquids.

    PubMed

    Lee, Alpha A; Kondrat, Svyatoslav; Vella, Dominic; Goriely, Alain

    2015-09-01

    A gap in understanding the link between continuum theories of ion transport in ionic liquids and the underlying microscopic dynamics has hindered the development of frameworks for transport phenomena in these concentrated electrolytes. Here, we construct a continuum theory for ion transport in ionic liquids by coarse graining a simple exclusion process of interacting particles on a lattice. The resulting dynamical equations can be written as a gradient flow with a mobility matrix that vanishes at high densities. This form of the mobility matrix gives rise to a charging behavior that is different to the one known for electrolytic solutions, but which agrees qualitatively with the phenomenology observed in experiments and simulations. PMID:26382685

  7. Dissolution enthalpies of cellulose in ionic liquids.

    PubMed

    Parviainen, Helena; Parviainen, Arno; Virtanen, Tommi; Kilpeläinen, Ilkka; Ahvenainen, Patrik; Serimaa, Ritva; Grönqvist, Stina; Maloney, Thaddeus; Maunu, Sirkka Liisa

    2014-11-26

    In this work, interactions between cellulose and ionic liquids were studied calorimetrically and by optical microscopy. Two novel ionic liquids (1,5-Diazabicyclo[4.3.0]non-5-enium propionate and N-methyl-1,5-diazabicyclo[4.3.0]non-5-enium dimethyl phosphate) and 1-ethyl-3-methylimidazolium acetate-water mixtures were used as solvents. Optical microscopy served in finding the extent of dissolution and identifying the dissolution pattern of the cellulose sample. Calorimetric studies identified a peak relating to dissolution of cellulose in solvent. The transition did, however, not indicate complete dissolution, but rather dissolution inside fibre or fibrils. This method was used to study differences between four cellulose samples with different pretreatment or origins. PMID:25256460

  8. 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

  9. 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.

  10. Structural modifications of nucleosides in ionic liquids

    PubMed Central

    Kumar, Vineet; Parmar, Virinder S.; Malhotra, Sanjay V.

    2011-01-01

    Nucleoside chemistry represents an important research area for drug discovery, as many nucleoside analogs are prominent drugs and have been widely applied for cancer and viral chemotherapy. However, the synthesis of modified nucleosides presents a major challenge, which is further aggravated by poor solubility of these compounds in common organic solvents. Most of the currently available methods for nucleoside modification employ toxic high boiling solvents; require long reaction time and tedious workup methods. As such, there is constant effort to develop process chemistry in alternative medium to limit the use of organic solvents that are hazardous to the environment and can be deleterious to human health. One such approach is to use ionic liquids, which are ‘designer materials’ with unique and tunable physico-chemical properties. Studies have shown that methodologies using ionic liquids are highly efficient and convenient for the synthesis of nucleoside analogs, as demonstrated by the preparation of pharmaceutically important anti-viral drugs. This article summarizes recent efforts on nucleoside modification using ionic liquids. PMID:20178825

  11. 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

  12. 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

  13. 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

  14. Correlating morphology to dc conductivity in polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

    Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

  15. Fixed Junction Photovoltaic Devices Based On Polymerizable Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Limanek, Austin; Leger, Janelle, , Dr.

    Recently, polymer-based photovoltaic devices (PPVs) have received significant attention as a possible affordable, large area and flexible solar energy technology. In particular, research on chemically fixed p-i-n junctions in polymer photovoltaic devices has shown promising results. These devices are composed of ionic monomers in a polymer matrix sandwiched between two electrodes. When a potential is applied, the ionic monomers migrate towards their corresponding electrodes, enabling electrochemical doping of the polymer. This leads to the formation of bonds between the polymer and ionic monomers, resulting in the formation of a chemically fixed p-i-n junction. However, early devices suffered from long charging times and low overall response. This has been attributed to the low phase compatibility between the ionic monomers and the polymer. It has been shown for light-emitting electrochemical cells, replacing the ionic monomers with polymerizable ionic liquids (PILs) mitigates these challenges. We will present the use of PILs as the dopant in fixed junction PPV devices. Preliminary devices demonstrate significantly improved performance, decreased charging times, and high open circuit voltages. This research supported by the National Science Foundation DMR-1057209.

  16. 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.

  17. Ionic liquid supported on an electrodeposited polycarbazole film for the headspace solid-phase microextraction and gas chromatography determination of aromatic esters.

    PubMed

    Feng, Yuanyuan; Zhao, Faqiong; Zeng, Baizhao

    2015-05-01

    A polycarbazole film was electrodeposited on a stainless-steel wire from a solution of N,N-dimethylformamide/propylene carbonate (1:9 v/v) containing 0.10 M carbazole and 0.10 M tetrabutylammonium perchlorate. The obtained polycarbazole fiber was immersed into an ionic liquid (1-hydroxyethyl-3-methyl imidazolium bis[(trifluoromethyl)sulfonyl]imide) solution (in dimethylsulfoxide) for 30 min, followed by drying under an infrared lamp. The resulting polycarbazole/ionic liquid fiber was applied to the headspace solid-phase microextraction and determination of aromatic esters by coupling with gas chromatography and flame ionization detection. Under the optimized conditions, the limits of detection were below 61 ng/L (S/N = 3) and the linear ranges were 0.061-500 μg/L with correlation coefficients above 0.9876. The relative standard deviations were below 4.8% (n = 5) for a single fiber, and below 9.9% for multi-fiber (n = 4). This fiber also exhibited good stability. It could be used for more than 160 times of headspace solid-phase microextraction and could withstand a high temperature up to 350°C. PMID:25676087

  18. Supported liquid membranes

    SciTech Connect

    Danesi, P.R.

    1984-01-01

    The possibility of utilizing thin layers of organic solutions of solvent extraction reagents, immobilized on microporous inert supports interposed between two aqueous solutions, for selectively removing metal ions from a mixture represents an attractive alternative to liquid-liquid extraction. A detailed knowledge of the liquid-liquid extraction equilibria and mass transfer kinetics is required to understand and to describe quantitatively the rate laws which control the permeation of metal species through Supported Liquid Membranes (SLM) and to exploit them for separation processes. This paper attempts to understand the mechanism of transport through SLM.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. Evaporation from an ionic liquid emulsion.

    PubMed

    Friberg, Stig E

    2007-03-15

    The conditions during evaporation in a liquid crystal-in-ionic liquid microemulsion (LC/microEm) were estimated using the phase diagram of the system. The equations for selected tie lines were established and the coordinates calculated for the sites, at which the evaporation lines crossed the tie lines. These values combined with the coordinates for the phases connecting the tie lines were used to calculate the amounts and the composition of the fractions of the two phases present in the emulsion during the evaporation. One of the emulsion phases was a lamellar liquid crystal and high energy emulsification would lead to the liquid crystal being disrupted to form vesicles. Such a system tenders a unique opportunity to study the interaction between vesicles and normal micelles, which gradually change to inverse micelles over bi-continuous structures. The amount of vesicles in the liquid phase versus the fraction liquid crystal was calculated for two extreme cases of vesicle core size and shell thickness. The limit of evaporation while retaining the vesicle structure was calculated for emulsions of different original compositions assuming the minimum continuous liquid phase to be 50% of the emulsion. PMID:17207810

  4. 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

  5. Magnetic microemulsions based on magnetic ionic liquids.

    PubMed

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

    2012-11-28

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

  6. Controlling Oxygen Vacancy Creation In Ionic Liquid Gated Vanadate Nanostructures

    NASA Astrophysics Data System (ADS)

    Kilcoyne, Colin; Singh, Sujay; Horrocks, Gregory; Marley, Peter; Banerjee, Sarbajit; Sambandamurthy, G.

    Vanadium dioxide (VO2) is a correlated material with a transition from a monoclinic insulator to a rutile metal at ~ 340 K. Through ionic liquid gating, oxygen vacancies can be electrochemically induced in VO2 and it is found that the vacancies formation is greatly facilitated in the rutile phase, leading to the suppression of the metal-insulator transition. The reversibility, the rate and kinetics of the electrochemical reaction can be readily controlled with the gate voltage sweeps suggesting a potential defect engineering route to tune the electrical and structural properties of VO2. Vanadium pentoxide (V2O5) is a related system with diverse structural and electronic phases that can be obtained by intercalation of various cations. The electrochemical role of ionic liquid gating in creating new phases and modulating conductance in exfoliated thin flakes of V2O5 will also be presented. This work is supported by NSF DMR 0847324.

  7. Electrotunable Lubricity with Ionic Liquid Nanoscale Films

    PubMed Central

    Fajardo, O. Y.; Bresme, F.; Kornyshev, A. A.; Urbakh, M.

    2015-01-01

    One of the main challenges in tribology is finding the way for an in situ control of friction without changing the lubricant. One of the ways for such control is via the application of electric fields. In this respect a promising new class of lubricants is ionic liquids, which are solvent-free electrolytes, and their properties should be most strongly affected by applied voltage. Based on a minimal physical model, our study elucidates the connection between the voltage effect on the structure of the ionic liquid layers and their lubricating properties. It reveals two mechanisms of variation of the friction force with the surface charge density, consistent with recent AFM measurements, namely via the (i) charge effect on normal and in-plane ordering in the film and (ii) swapping between anion and cation layers at the surfaces. We formulate conditions that would warrant low friction coefficients and prevent wear by resisting “squeezing-out” of the liquid under compression. These results give a background for controllable variation of friction. PMID:25572127

  8. Ionic Liquid Structure-Induced Effects on Organic Reactions

    NASA Astrophysics Data System (ADS)

    Stark, Annegret

    Understanding the ways in which the constituents of ionic liquids, i.e. the type of cation, its substitution, and the type of anion chosen, interact with reactants is prerequisite to deliberately designing an ionic liquid solvent with optimum performance. Several approaches, including physico-chemical and spectroscopic measurements and computational studies of binary ionic liquid-substrate mixtures have been presented that investigate the strength of interactions.

  9. Ionic Liquid assisted Synthesis of Zeolite-TON

    PubMed Central

    Tian, Yuyang; McPherson, Matthew J; Wheatley, Paul S; Morris, Russell E

    2014-01-01

    An ionic liquid assisted strategy for the synthesis of zeolitic material is reported. This strategy is a solid state synthetic method and the ionic liquid is employed as structure directing agent. A TON-type zeolite, which contains one-dimensional 10-member-ring, is successfully synthesized with the assistance of the ionic liquid, 1-ethyl-3-methylimidazolium bromide. This finding improves our understanding about the challenge of ionothermally synthesizing siliceous and aluminosilicate zeolites. PMID:26213423

  10. 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.

  11. 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.

  12. Highly luminescent and color-tunable salicylate ionic liquids

    DOE PAGESBeta

    Campbell, Paul S.; Yang, Mei; Pitz, Demian; Cybinska, Joanna; Mudring, Anja -Verena

    2014-03-11

    High quantum yields of up to 40.5 % can be achieved in salicylate-bearing ionic liquids. A range of these ionic liquids have been synthesized and their photoluminescent properties studied in detail. The differences noted can be related back to the structure of the ionic liquid cation and possible interionic interactions. It is found that shifts of emission, particularly in the pyridinium-based ionic liquids, can be related to cation–anion pairing interactions. Furthermore, facile and controlled emission color mixing is demonstrated through combining different ILs, with emission colors ranging from blue to yellow.

  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. 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.

  15. Determination of solubility parameters of ionic liquids and ionic liquid/solvent mixtures from intrinsic viscosity.

    PubMed

    Weerachanchai, Piyarat; Wong, Yuewen; Lim, Kok Hwa; Tan, Timothy Thatt Yang; Lee, Jong-Min

    2014-11-10

    The total and partial solubility parameters (dispersion, polar and hydrogen-bonding solubility parameters) of ten ionic liquids were determined. Intrinsic viscosity approaches were used that encompassed a one-dimensional method (1D-Method), and two different three-dimensional methods (3D-Method1 and 3D-Method2). The effect of solvent type, the dimethylacetamide (DMA) fraction in the ionic liquid, and dissolution temperature on solubility parameters were also investigated. For all types of effect, both the 1D-Method and 3D-Method2 present the same trend in the total solubility parameter. The partial solubility parameters are influenced by the cation and anion of the ionic liquid. Considering the effect on partial solubility parameters of the solvent type in the ionic liquid, it was observed that in both 3D methods, the dispersion and polar parameters of a 1-ethyl-3-methylimidazolium acetate/solvent (60:40 vol %) mixture tend to increase as the total solubility parameter of the solvent increases. PMID:25145759

  16. 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.

  17. Extraction of proteins with ionic liquid aqueous two-phase system based on guanidine ionic liquid.

    PubMed

    Zeng, Qun; Wang, Yuzhi; Li, Na; Huang, Xiu; Ding, Xueqin; Lin, Xiao; Huang, Songyun; Liu, Xiaojie

    2013-11-15

    Eight kinds of green ionic liquids were synthesized, and an ionic liquid aqueous two-phase system (ILATPS) based on 1,1,3,3-tetramethylguandine acrylate (TMGA) guanidine ionic liquid was first time studied for the extraction of proteins. Single factor experiments proved that the extraction efficiency of bovine serum albumin (BSA) was influenced by the mass of IL, K2HPO4 and BSA, also related to the separation time and temperature. The optimum conditions were determined through orthogonal experiment by the five factors described above. The results showed that under the optimum conditions, the extraction efficiency could reach up to 99.6243%. The relative standard deviations (RSD) of extraction efficiencies in precision experiment, repeatability experiment and stability experiment were 0.8156% (n=5), 1.6173% (n=5) and 1.6292% (n=5), respectively. UV-vis and FT-IR spectra confirmed that there were no chemical interactions between BSA and ionic liquid in the extraction process, and the conformation of the protein was not changed after extraction. The conductivity, DLS and TEM were combined to investigate the microstructure of the top phase and the possible mechanism for the extraction. The results showed that hydrophobic interaction, hydrogen bonding interaction and the salt out effect played important roles in the transferring process, and the aggregation and embrace phenomenon was the main driving force for the separation. All these results proved that guanidine ionic liquid-based ATPSs have the potential to offer new possibility in the extraction of proteins. PMID:24148423

  18. 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

  19. Predictive thermodynamics for ionic solids and liquids.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

    The application of thermodynamics is simple, even if the theory may appear intimidating. We describe tools, developed over recent years, which make it easy to estimate often elusive thermodynamic parameter values, generally (but not exclusively) for ionic materials, both solid and liquid, as well as for their solid hydrates and solvates. The tools are termed volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR), supplemented by the simple salt approximation (SSA) and single-ion values for volume, Vm, heat capacity, , entropy, , formation enthalpy, ΔfH°, and Gibbs formation energy, ΔfG°. These tools can be applied to provide values of thermodynamic and thermomechanical properties such as standard enthalpy of formation, ΔfH°, standard entropy, , heat capacity, Cp, Gibbs function of formation, ΔfG°, lattice potential energy, UPOT, isothermal expansion coefficient, α, and isothermal compressibility, β, and used to suggest the thermodynamic feasibility of reactions among condensed ionic phases. Because many of these methods yield results largely independent of crystal structure, they have been successfully extended to the important and developing class of ionic liquids as well as to new and hypothesised materials. Finally, these predictive methods are illustrated by application to K2SnCl6, for which known experimental results are available for comparison. A selection of applications of VBT and TDR is presented which have enabled input, usually in the form of thermodynamics, to be brought to bear on a range of topical problems. Perhaps the most significant advantage of VBT and TDR methods is their inherent simplicity in that they do not require a high level of computational expertise nor expensive high-performance computation tools - a spreadsheet will usually suffice - yet the techniques are extremely powerful and accessible to non-experts. The connection between formula unit volume, Vm, and standard thermodynamic parameters represents a

  20. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  1. Design of ionic liquids for lipase purification.

    PubMed

    Ventura, Sónia P M; Sousa, Sílvia G; Freire, Mara G; Serafim, Luísa S; Lima, Alvaro S; Coutinho, João A P

    2011-09-15

    Aqueous two-phase systems (ATPS) are considered as efficient downstream processing techniques in the production and purification of enzymes, since they can be considered harmless to biomolecules due to their high water content and due to the possibility of maintaining a neutral pH value in the medium. A recent type of alternative ATPS is based on hydrophilic ionic liquids (ILs) and salting-out inducing salts. The aim of this work was to study the lipase (Candida antarctica lipase B - CaLB) partitioning in several ATPS composed of ionic liquids (ILs) and inorganic salts, and to identify the best IL for the enzyme purification. For that purpose a wide range of IL cations and anions, and some of their combinations were studied. For each system the enzyme partitioning between the two phases was measured and the purification factors and enzyme recoveries were determined. The results indicate that the lipase maximum purification and recovery were obtained for cations with a C(8) side alkyl chain, the [N(CN)(2)] anion and ILs belonging to the pyridinium family. However, the highest purification parameters were observed for 1-methyl-3-octylimidazolium chloride [C(8)mim]Cl, suggesting that the IL extraction capability does not result from a cumulative character of the individual characteristics of ILs. The results indicate that the IL based ATPS have an improved performance in the lipase purification and recovery. PMID:21852207

  2. 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

  3. Glass transition of ionic liquids under high pressure

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    PubMed

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

    2014-05-19

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

  5. 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

  6. Ionic liquid crosslinkers for chiral imprinted nanoGUMBOS.

    PubMed

    Hamdan, Suzana; Moore, Leonard; Lejeune, Jason; Hasan, Farhana; Carlisle, Trevor K; Bara, Jason E; Gin, D L; LaFrate, Andrew L; Noble, R D; Spivak, David A; Warner, Isiah M

    2016-02-01

    Molecularly imprinted polymers (MIPs) are an important class of selective materials for molecular specific sensors and separations. Molecular imprinting using non-covalent interactions in aqueous conditions still remains a difficult challenge due to interruption of hydrogen-bonding or electrostatic interactions water. Newly developed crosslinking ionic liquids are demonstrated herein to overcome problems of synthesizing aqueous MIPs, adding to previous examples of ionic liquids used as monomers in non-aqueous conditions or used as MIP solvents. Vinylimidazole ionic liquid crosslinkers were synthesized and subsequently explored as matrix supports for fabrication of molecularly imprinted polymeric nanoGUMBOS (nanoparticles derived from a group of uniform materials based on organic salts). Each of the four crosslinkers incorporated a unique functional spacer between the vinylimidazole groups, and the performance of the corresponding molecularly imprinted polymers was evaluated using chiral recognition as the diagnostic. High uptake values for l-tryptophan were found in the 13-87μmol/g range; and chiral recognition was determined via binding ratios of l-tryptophan over d-tryptophan that ranged from 5:1 to 13:1 for polymers made using different crosslinkers. Not only are these materials good for chiral recognition, but the results highlight the utility of these materials for imprinting aqueous templates such as biological targets for theranostic agents. PMID:26513734

  7. 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.

  8. Absorption and Oxidation of Nitrogen Oxide in Ionic Liquids.

    PubMed

    Kunov-Kruse, Andreas J; Thomassen, Peter L; Riisager, Anders; Mossin, Susanne; Fehrmann, Rasmus

    2016-08-01

    A new strategy for capturing nitrogen oxide, NO, from the gas phase is presented. Dilute NO gas is removed from the gas phase by ionic liquids under ambient conditions. The nitrate anion of the ionic liquid catalyzes the oxidation of NO to nitric acid by atmospheric oxygen in the presence of water. The nitric acid is absorbed in the ionic liquid up to approximately one mole HNO3 per mole of the ionic liquid due to the formation of hydrogen bonds. The nitric acid can be desorbed by heating, thereby regenerating the ionic liquid with excellent reproducibility. Here, time-resolved in-situ spectroscopic investigations of the reaction and products are presented. The procedure reveals a new vision for removing the pollutant NO by absorption into a non-volatile liquid and converting it into a useful bulk chemical, that is, HNO3 . PMID:27384885

  9. Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

    Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an

  10. Tetraalkylphosphonium polyoxometalates : Electroactive, 'task-specific' ionic liquids.

    SciTech Connect

    Rickert, P. G.; Antonio, M. R.; Firestone, M. A.; Kubatko, K-A.; Szreder, T.; Wishart, J. F.; Dietz, M. L.; BNL; Univ. of Miami

    2007-01-01

    The pairing of selected polyoxometalate (POM) anions with appropriate tetraalkylphosphonium cations is shown to yield an original family of ionic liquids, among them an ambient-temperature 'liquid POM.'

  11. 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.

  12. 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…

  13. Polarity of the interface in ionic liquid in oil microemulsions.

    PubMed

    Andújar-Matalobos, María; García-Río, Luis; López-García, Susana; Rodríguez-Dafonte, Pedro

    2011-11-01

    Ionic liquid based microemulsions were characterized by absorption solvatochromic shifts, (1)H NMR and kinetic measurements in order to investigate the properties of the ionic liquid within the restricted geometry provided by microemulsions and the interactions of the ionic liquid with the interface. Experimental results show a significant difference between the interfaces of normal water and the new ionic liquid microemulsions. Absorption solvatochromic shift experiments and kinetic studies on the aminolysis of 4-nitrophenyl laurate by n-decylamine show that the polarity at the interface of the ionic liquid in oil microemulsions (IL/O) is higher than at the interface of water in oil microemulsions (W/O) despite the fact that the polarity of [bmim][BF(4)(-)] is lower than the polarity of water. (1)H NMR experiments showed that an increase in the ionic liquid content of the microemulsion led to an increase in the interaction between [bmim][BF(4)(-)] and TX-100. The reason for the higher polarity of the microemulsions with the ionic liquid can be explained in terms of the incorporation of higher levels of the ionic liquid at the interface of the microemulsions, as compared to water in the traditional systems. PMID:21820124

  14. 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.

  15. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

    SciTech Connect

    Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W.; Husson, Pascale; Costa Gomes, Margarida F.; Greenbaum, Steven G.

    2015-08-14

    We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyze the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies.

  16. 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

  17. Interionic Interactions in Imidazolium-Based Ionic Liquids: The Role of the C2-Position Revealed by Raman Scattering and Supported by IR and NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Noack, Kristina; Paape, Natalia; Kiefer, Johannes; Wasserscheid, Peter; Leipertz, Alfred

    2010-08-01

    Intermolecular interactions determine the state of aggregation of a substance at given temperature. Based on that, changes in intermolecular interactions can lead to microscopic reordering which may be observed macroscopically in terms of altered physicochemical properties. Especially, when chemicals are employed in technical processes, it is important to control and regulate their properties to guarantee product quality. A special group of chemical substances increasingly gaining interest in the field of chemical and process engineering are room temperature ionic liquids (RTILs). In general, RTILs are organic salts with melting points "below the boiling point of water". The variety of possible combinations of cations and anions lead to a wide range of chemical and thermo-physical properties. In fact, it is possible to tune their properties by adjusting the ratio of Coulomb and van der Waals interactions. However, because it is hardly possible to investigate a reasonable fraction of the potential cation-anion combinations, a molecular-based understanding of their properties is crucial to make a rational design possible. In this regard vibrational spectroscopy has proven to be very beneficial for structural analysis and the investigation of interionic and intermolecular interactions. Therein, especially Raman spectroscopy shows a significant advantage of being insensitive to water interference and it is widely applied in the field of ionic liquids. Among others the 1-alkyl-3-methylimidazolium [RMIM] based ILs have been employed as model ILs in structural analysis, and most vibrational studies available in literature have been carried out investigating this kind of ILs. In contrast, spectroscopic data and calculations of C2-methylated 1,2-dialkyl-3-methylimidazolium based ILs, are available to a much lesser extend. The substitution in the C2 position in those ILs disrupts the main hydrogen-bonding interaction between the cation and the anion and is expected to lead

  18. Intermolecular vibrations and fast relaxations in supercooled ionic liquids

    NASA Astrophysics Data System (ADS)

    Ribeiro, Mauro C. C.

    2011-06-01

    Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < ω < 100 cm-1) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (˜19 Å) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids.

  19. 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.

  20. 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.

  1. 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).

  2. Microregion detection of ionic liquid microemulsions.

    PubMed

    Gao, Yanan; Wang, Suqing; Zheng, Liqiang; Han, Shuaibing; Zhang, Xuan; Lu, Deming; Yu, Li; Ji, Yongqiang; Zhang, Gaoyong

    2006-09-15

    Nonaqueous ionic liquid (IL) microemulsion consisting of IL, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), surfactant TX-100, and toluene was prepared and the phase behavior of the ternary system was investigated. Electrical conductivity measurement was used for investigating the microregions of the nonaqueous IL microemulsions. On the basis of the percolation theory, the bmimBF(4)-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF(4) (O/IL) microregions of the microemulsions were successfully identified using insulative toluene as the titration phase. However, this method was invalid when conductive bmimBF(4) acted as the titration phase. The microregions obtained by conductivity measurements were further proved by electrochemical cyclic voltammetry experiments. The results indicated that the conductivity method was feasible for identifying microstructures of the nonaqueous IL microemulsions. PMID:16765365

  3. 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

  4. 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.

  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. 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

  7. Imidazolium-based ionic liquids grafted on solid surfaces.

    PubMed

    Xin, Bingwei; Hao, Jingcheng

    2014-01-01

    Supported ionic liquids (SILs), which refer to ionic liquids (ILs) immobilized on supports, are among the most important derivatives of ILs. The immobilization process of ILs can transfer their desired properties to substrates. Combination of the advantages of ILs with those of support materials will derive novel performances while retaining properties of both moieties. SILs have been widely applied in almost all of fields involving ILs, and have brought about drastic expansion of the ionic liquid area. As green media in organic catalytic reactions, based on utilizing the ability of ILs to stabilize the catalysts, they have many advantages over free ILs, including avoiding the leaching of ILs, reducing their amount, and improving the recoverability and reusability of both themselves and catalysts. This has critical significance from both environmental and economical points of view. As novel functional materials in surface science and material chemistry, SILs are ideal surface modifying agents. They can modify and improve the properties of solids, such as wettability, lubricating property, separation efficiency and electrochemical response. With the achievements in the field of ILs, using magnetic nanoparticles (MNPs) to SILs has drawn increasing attention in catalytic reactions and separation technologies, and achieved substantial progress. The combination of MNPs and ILs renders magnetic SILs, which exhibit the unique properties of ILs as well as facile separation by an external magnetic field. In this article, we focus on imidazolium-based ILs covalently grafted to non-porous and porous inorganic materials. The excellent stability and durability of this kind of SILs offer a great advantage compared with free ILs and IL films physically adsorbed on substrates without covalent bonds. Including examples from our own research, we overview mainly the applications and achievements of covalent-linked SILs in catalytic reactions, surface modification, separation

  8. Optimization of covalent immobilization of Trichoderma reesei cellulase onto modified ReliZyme HA403 and Sepabeads EC-EP supports for cellulose hydrolysis, in buffer and ionic liquids/buffer media.

    PubMed

    Bilgin, Ramazan; Yalcin, M Serkan; Yildirim, Deniz

    2016-08-01

    The covalent immobilization of Trichoderma reesei cellulase onto modified ReliZyme HA403 and Sepabeads EC-EP supports were carried out. The optimal immobilization conditions were determined using response surface methodology. The hydrolysis of cellulose using the free and immobilized cellulase preparations in ionic liquids (IL) using cosolvents was investigated. The hydrolytic activities in buffer medium containing 25% (v/v) of 1-butyl-3-methylimidazolium hexafluorophosphate were around 2.6-, 1.6-, and 5.5-fold higher than the activities in buffer medium. The retained initial activities were 32% and 57%, respectively for cellulase preparations immobilized onto Sepabeads EC-EP support and onto modified ReliZyme HA403 support after 5 reuses. PMID:25811997

  9. Femtosecond solvation dynamics in a neat ionic liquid and ionic liquid microemulsion: excitation wavelength dependence.

    PubMed

    Adhikari, Aniruddha; Sahu, Kalyanasis; Dey, Shantanu; Ghosh, Subhadip; Mandal, Ujjwal; Bhattacharyya, Kankan

    2007-11-01

    Solvation dynamics in a neat ionic liquid, 1-pentyl-3-methyl-imidazolium tetra-flouroborate ([pmim][BF4]) and its microemulsion in Triton X-100 (TX-100)/benzene is studied using femtosecond up-conversion. In both the neat ionic liquid and the microemulsion, the solvation dynamics is found to depend on excitation wavelength (lambda(ex)). The lambda(ex) dependence is attributed to structural heterogeneity in neat ionic liquid (IL) and in IL microemulsion. In neat IL, the heterogeneity arises from clustering of the pentyl groups which are surrounded by a network of cation and anions. Such a nanostructural organization is predicted in many recent simulations and observed recently in an X-ray diffraction study. In an IL microemulsion, the surfactant (TX-100) molecules aggregate in form of a nonpolar peripheral shell around the polar pool of IL. The micro-environment in such an assembly varies drastically over a short distance. The dynamic solvent shift (and average solvation time) in neat IL as well as in IL microemulsions decreases markedly as lambda(ex) increases from 375 to 435 nm. In a [pmim][BF4]/water/TX-100/benzene quaternary microemulsion, the solvation dynamics is slower than that in a microemulsion without water. This is ascribed to the smaller size of the water containing microemulsion. The anisotropy decay in an IL microemulsion is found to be faster than that in neat IL. PMID:17944511

  10. An ionic liquid process for mercury removal from natural gas.

    PubMed

    Abai, Mahpuzah; Atkins, Martin P; Hassan, Amiruddin; Holbrey, John D; Kuah, Yongcheun; Nockemann, Peter; Oliferenko, Alexander A; Plechkova, Natalia V; Rafeen, Syamzari; Rahman, Adam A; Ramli, Rafin; Shariff, Shahidah M; Seddon, Kenneth R; Srinivasan, Geetha; Zou, Yiran

    2015-05-14

    Efficient scrubbing of mercury vapour from natural gas streams has been demonstrated both in the laboratory and on an industrial scale, using chlorocuprate(II) ionic liquids impregnated on high surface area porous solid supports, resulting in the effective removal of mercury vapour from natural gas streams. This material has been commercialised for use within the petroleum gas production industry, and has currently been running continuously for three years on a natural gas plant in Malaysia. Here we report on the chemistry underlying this process, and demonstrate the transfer of this technology from gram to ton scale. PMID:25722100

  11. Particle aggregation mechanisms in ionic liquids.

    PubMed

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

    2014-05-28

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

  12. Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

    NASA Astrophysics Data System (ADS)

    Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

    2011-04-01

    Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

  13. 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.

  14. 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.

  15. Proton Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan; Tyagi, Madhu; Reimer, Jeffrey; Segalman, Rachel

    2011-03-01

    Nanostructured block copolymer/ionic liquid mixtures are of interest for creating membranes having high proton conductivity coupled with high thermal stability. In these mixtures, it is anticipated that nanoconfinement to block copolymer domains will affect ionic liquid proton transport properties. Using pulsed-field gradient NMR and quasi-elastic neutron scattering, this relationship has been investigated for mixtures of poly(styrene-b- 2-vinylpyridine) (S2VP) with ionic liquids composed of imidazole and bis(trifluoromethane)sulfonimide (HTFSI), where the ionic liquids selectively reside in the P2VP domains of the block copolymer. Proton mobility is highest in the neat ionic liquids when there is an excess of imidazole compared to HTFSI due to proton hopping between hydrogen-bonded imidazoles. As predicted, the amount of proton hopping can be tuned by nanoconfinement, as evidenced by the finding that a lamellar mixture of an imidazole- excess ionic liquid with S2VP has greater proton mobility than a corresponding disordered mixture of the ionic liquid with P2VP homopolymer.

  16. 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

  17. 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

  18. 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

  19. Ultrasound-assisted ionic liquid-based microextraction combined with least squares support vector machines regression for the simultaneous determination of aluminum, gallium, and indium in water and coal samples.

    PubMed

    Ghasemi, Jahan B; Zolfonoun, Ehsan

    2012-06-01

    A new simple and rapid ultrasound-assisted ionic liquid-based microextraction method was applied to preconcentrate aluminum(III), gallium(III), and indium(III) ions from water samples as a prior step to their simultaneous spectrophotometric determination using least squares support vector machines regression. In the novel procedure, 1-hexyl-3-methylimidazolium hexafluorophosphate [C(6)MIM][PF(6)] was dispersed into the aqueous sample solution as fine droplets by ultrasonication, and the analytes were extracted into the ionic liquid phase after complexation with 1,2,5,8-tetrahydroxy anthraquinone (quinalizarine). After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom glass centrifuge tube. The detection limits for Al(III), Ga(III), and In(III) were 1.70, 2.02, and 2.06 ng mL(-1), respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of ten replicates, was below 3.2% for all elements. The method was successfully applied for the determination of Al(III), Ga(III), and In(III) in real samples. PMID:21789531

  20. Inorganic or organic azide-containing hypergolic ionic liquids.

    PubMed

    Joo, Young-Hyuk; Gao, Haixiang; Zhang, Yanqiang; Shreeve, Jean'ne M

    2010-04-01

    Recently extensive research has focused on replacing toxic hydrazine, monomethylhydrazine, and unsymmetrical dimethylhydrazine as liquid propellant fuels. 2-Azido-N,N-dimethylethylamine (1) is a good candidate to replace hydrazine derivatives in certain hypergolic fuel applications. Energetic ionic liquids that contain the 2-azido-N,N,N-trimethylethylammonium cation with nitrocyanamide, dicyanamide, dinitramide, or azide anion have been successfully synthesized in good yields by metathesis reactions. Ionic liquids have received considerable attention as energetic materials. The replacement of hydrazine with tertiary ammonium salts is especially attractive since many ionic liquids are models for green chemistry. In this work, new azide-functionalized ionic liquids are demonstrated to exhibit hypergolic activity with such oxidizers as 100% nitric acid or nitrogen tetraoxide (NTO). PMID:20175509

  1. Solvatochromic Study on Binary Solvent Mixtures with Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Koel, Mihkel

    2008-08-01

    Solvent effects on 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate [ET (33) dye] and 7- diethylamino-3,4-benzophenoxazine-2-one (Nile Red) in binary mixtures of organic solvents (acetone, acetonitrile, propylene carbonate, methanol and ethane-1,2-diol) with 1,3-dialkyl imidazoliumbased ionic liquids were studied by UV-visible spectroscopy. Highly nonlinear behaviour of mixtures of alcohols and ionic liquids was found. A preferential solvation model was applied to the data obtained on solvatochromic shifts over the entire mixing range. It is fitting the data well for alcohol mixtures and for other solvent mixtures with different ionic liquids.

  2. 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

  3. 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.

  4. 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

  5. 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

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

    PubMed

    Xu, Yiting; Zheng, Qiang; Song, Yihu

    2015-08-14

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

  7. Charge trapping in imidazolium ionic liquids.

    PubMed

    Shkrob, Ilya A; Wishart, James F

    2009-04-23

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

  8. 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

  9. 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

  10. 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

  11. 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).

  12. Nanodroplet cluster formation in ionic liquid microemulsions.

    PubMed

    Gao, Yanan; Voigt, Andreas; Hilfert, Liane; Sundmacher, Kai

    2008-08-01

    A common ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), is used as polar solvent to induce the formation of a reverse bmimBF(4)-in-toluene IL microemulsion with the aid of the nonionic surfactant Triton X-100. The swelling process of the microemulsion droplets by increasing bmimBF(4) content is detected by dynamic light scattering (DLS), conductivity, UV/Vis spectroscopy, and freeze-fracture transmission electron microscopy (FF-TEM). The results show that the microemulsion droplets initially formed are enlarged by the addition of bmimBF(4). However, successive addition of bmimBF(4) lead to the appearance of large-sized microemulsion droplet clusters (200-400 nm). NMR spectroscopic analysis reveal that the special structures and properties of bmimBF(4) and Triton X-100 together with the polar nature of toluene contribute to the formation of such self-assemblies. These unique self-assembled structures of IL-based microemulsion droplet clusters may have some unusual and unique properties with a number of interesting possibilities for potential applications. PMID:18576451

  13. 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.

  14. Ionic Liquids Can Permanently Modify Porous Silicon Surface Chemistry.

    PubMed

    Trivedi, Shruti; Coombs, Sidney G; Wagle, Durgesh V; Bhawawet, Nakara; Baker, Gary A; Bright, Frank V

    2016-08-01

    To develop ionic liquid/porous silicon (IL/pSi) microarrays we have contact pin-printed 20 hydrophobic and hydrophilic ionic liquids onto as-prepared, hydrogen-passivated porous silicon (ap-pSi) and then determined the individual IL spot size, shape and associated pSi surface chemistry. The results reveal that the hydrophobic ionic liquids oxidize the ap-pSi slightly. In contrast, the hydrophilic ionic liquids lead to heavily oxidized pSi (i.e., ox-pSi). The strong oxidation arises from residual water within the hydrophilic ILs that is delivered from these ILs into the ap-pSi matrix causing oxidation. This phenomenon is less of an issue in the hydrophobic ILs because their water solubility is substantially lower. PMID:27405109

  15. 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.

  16. 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

  17. 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

  18. SYNTHESIS AND ANTIMICROBIAL PROPERTIES OF NEW MANDELATE IONIC LIQUIDS.

    PubMed

    Wiśniewska, Anna; Lipińsk, Piotr F J; Woźniak, Krzysztof; Sanjuan-Szklarz, Fabiola; Cieniecka-Rosłonkiewicz, Anna; Michalczyk, Alicja; Dabrowski, Zbigniew; Kulig-Adamiak, Anna; Matalińska, Joanna; Leś, Andrzej; Cybulski, Jacek

    2016-01-01

    Novel mandelate ionic liquids with quartenary ammonium cations were synthesized and characterized. The compounds exhibit antimicrobial activity and the most potent one is of similar efficacy against Gram+ bacteria as its counterpart chloride. On the other hand, the mandelates are much less active against Gram-bacteria and fungi. QSAR models suggest that, with respect to cation, their potency depends on lipophilicity. The synthesized ionic liquids are also quite cytotoxic against mammalian cells. PMID:27476289

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. 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 TlX(z)(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

  4. Ionic Liquids with Ammonium Cations as Lubricants or Additives

    SciTech Connect

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

    2006-01-01

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

  5. 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

  6. Novel applications of ionic liquids in materials processing

    NASA Astrophysics Data System (ADS)

    Reddy, Ramana G.

    2009-05-01

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

  7. 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

  8. 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.

  9. Modern ab initio valence bond theory calculations reveal charge shift bonding in protic ionic liquids.

    PubMed

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

    The nature of bonding interactions between the cation and the anion of an ionic liquid is at the heart of understanding ionic liquid properties. A particularly interesting case is a special class of ionic liquids known as protic ionic liquids. The extent of proton transfer in protic ionic liquids has been observed to vary according to the interacting species. Back proton transfer renders protic ionic liquids volatile and to be considered as inferior ionic liquids. We try to address this issue by employing modern ab initio valence bond theory calculations. The results indicate that the bonding in the cation and the anion of a prototypical ionic liquid, ethylammonium nitrate, is fundamentally different. It is neither characteristic of covalent/polar covalent bonding nor ionic bonding but rather charge shift bonding as a resonance hybrid of two competing ionic molecular electronic structure configurations. An investigation of other analogous protic ionic liquids reveals that this charge shift bonding seems to be a typical characteristic of protic ionic liquids while the ionic solid analogue compound ammonium nitrate has less charge shift bonding character as compared to protic ionic liquids. Further the extent of charge shift bonding character has been found to be congruent with the trends in many physicochemical properties such as melting point, conductivity, viscosity, and ionicity of the studied ionic liquids indicating that percentage charge shift character may serve as a key descriptor for large scale computational screening of ionic liquids with desired properties. PMID:27229870

  10. Ionic structure in liquids confined by dielectric interfaces.

    PubMed

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

    2015-11-21

    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. PMID:26590543

  11. 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.

  12. Ionic imbalance induced self-propulsion of liquid metals

    NASA Astrophysics Data System (ADS)

    Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

    2016-08-01

    Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

  13. Ionic imbalance induced self-propulsion of liquid metals.

    PubMed

    Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F; O'Mullane, Anthony P; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

    2016-01-01

    Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems. PMID:27488954

  14. Ionic imbalance induced self-propulsion of liquid metals

    PubMed Central

    Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-zadeh, Kourosh

    2016-01-01

    Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems. PMID:27488954

  15. 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

  16. 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

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

    SciTech Connect

    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.

  18. 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

  19. A New Volume-Based Approach for Predicting Thermophysical Behavior of Ionic Liquids and Ionic Liquid Crystals.

    PubMed

    Nelyubina, Yulia V; Shaplov, Alexander S; Lozinskaya, Elena I; Buzin, Mikhail I; Vygodskii, Yakov S

    2016-08-17

    Volume-based prediction of melting points and other properties of ionic liquids (ILs) relies on empirical relations with volumes of ions in these low-melting organic salts. Here we report an accurate way to ionic volumes by Bader's partitioning of electron densities from X-ray diffraction obtained via a simple database approach. For a series of 1-tetradecyl-3-methylimidazolium salts, the volumes of different anions are found to correlate linearly with melting points; larger anions giving lower-melting ILs. The volume-based concept is transferred to ionic liquid crystals (ILs that adopt liquid crystalline mesophases, ILCs) for predicting the domain of their existence from the knowledge of their constituents. For 1-alkyl-3-methylimidazolium ILCs, linear correlations of ionic volumes with the occurrence of LC mesophase and its stability are revealed, thus paving the way to rational design of ILCs by combining suitably sized ions. PMID:27479022

  20. 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.

  1. 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

  2. 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

  3. Thermal decomposition mechanisms of alkylimidazolium ionic liquids with cyano-functionalized anions.

    PubMed

    Chambreau, Steven D; Schenk, Adam C; Sheppard, Anna J; Yandek, Gregory R; Vaghjiani, Ghanshyam L; Maciejewski, John; Koh, Christine J; Golan, Amir; Leone, Stephen R

    2014-11-26

    Because of the unusually high heats of vaporization of room-temperature ionic liquids (RTILs), volatilization of RTILs through thermal decomposition and vaporization of the decomposition products can be significant. Upon heating of cyano-functionalized anionic RTILs in vacuum, their gaseous products were detected experimentally via tunable vacuum ultraviolet photoionization mass spectrometry performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Experimental evidence for di- and trialkylimidazolium cations and cyano-functionalized anionic RTILs confirms thermal decomposition occurs primarily through two pathways: deprotonation of the cation by the anion and dealkylation of the imidazolium cation by the anion. Secondary reactions include possible cyclization of the cation and C2 substitution on the imidazolium, and their proposed reaction mechanisms are introduced here. Additional evidence supporting these mechanisms was obtained using thermal gravimetric analysis-mass spectrometry, gas chromatography-mass spectrometry, and temperature-jump infrared spectroscopy. In order to predict the overall thermal stability in these ionic liquids, the ability to accurately calculate both the basicity of the anions and their nucleophilicity in the ionic liquid is critical. Both gas phase and condensed phase (generic ionic liquid (GIL) model) density functional theory calculations support the decomposition mechanisms, and the GIL model could provide a highly accurate means to determine thermal stabilities for ionic liquids in general. PMID:25381899

  4. Protein Structure and Stability in Neat Ionic Liquid

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  5. 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

  6. 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

  7. 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 solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis(trifluoromethylsulfonyl)imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C (temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis(trifluoromethylsulfonyl)imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations. PMID:17048916

  8. Preparation and evaluation of surface-bonded tricationic ionic liquid silica as stationary phases for high-performance liquid chromatography.

    PubMed

    Qiao, Lizhen; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2015-05-29

    Two tricationic ionic liquids were prepared and then bonded onto the surface of supporting silica materials through "thiol-ene" click chemistry as new stationary phases for high-performance liquid chromatography. The obtained columns of tricationic ionic liquids were evaluated respectively in the reversed-phase liquid chromatography (RPLC) mode and hydrophilic interaction liquid chromatography (HILIC) mode, and possess ideal column efficiency of 80,000 plates/m in the RPLC mode with naphthalene as the test solute. The tricationic ionic liquid stationary phases exhibit good hydrophobic and shape selectivity to hydrophobic compounds, and RPLC retention behavior with multiple interactions. In the HILIC mode, the retention and selectivity were evaluated through the efficient separation of nucleosides and bases as well as flavonoids, and the typical HILIC retention behavior was demonstrated by investigating retention changes of hydrophilic solutes with water volume fraction in mobile phase. The results show that the tricationic ionic liquid columns possess great prospect for applications in analysis of hydrophobic and hydrophilic samples. PMID:25890438

  9. Trace element partitioning between ionic crystal and liquid

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Philpotts, J. A.; Yin, L.

    1978-01-01

    The partitioning of trace elements between ionic crystals and the melt has been correlated with lattice energy of the host. The solid-liquid partition coefficient has been expressed in terms of the difference in relative ionic radius of the trace element and the homogeneous and heterogeneous strain of the host lattice. Predictions based on this model appear to be in general agreement with data for alkali nitrates and for rare-earth elements in natural garnet phenocrysts.

  10. Amphiphilic self-assembly of alkanols in protic ionic liquids.

    PubMed

    Jiang, Haihui Joy; FitzGerald, Paul A; Dolan, Andrew; Atkin, Rob; Warr, Gregory G

    2014-08-21

    Strong cohesive forces in protic ionic liquids (PILs) can induce a liquid nanostructure consisting of segregated polar and apolar domains. Small-angle X-ray scattering has shown that these forces can also induce medium chain length n-alkanols to self-assemble into micelle- and microemulsion-like structures in ethylammonium (EA(+)) and propylammonium (PA(+)) PILs, in contrast to their immiscibility with both water and ethanolammonium (EtA(+)) PILs. These binary mixtures are structured on two distinct length scales: one associated with the self-assembled n-alkanol aggregates and the other with the underlying liquid nanostructure. This suggests that EA(+) and PA(+) enable n-alkanol aggregation by acting as cosurfactants, which EtA(+) cannot do because its terminating hydroxyl renders the cation nonamphiphilic. The primary determining factor for miscibility and self-assembly is the ratio of alkyl chain lengths of the alkanol and PIL cation, modulated by the anion type. These results show how ILs can support the self-assembly of nontraditional amphiphiles and enable the creation of new forms of soft matter. PMID:25068766

  11. Morphology and charge transport in ammonium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Heres, Maximilian; Minutolo, Joseph; Shamblin, Jacob; Long, Maik; Berdzinski, Stefan; Stremel, Veronika; Sangoro, Joshua

    2015-03-01

    Ionic conduction, structural dynamics and morphology in a series of ammonium based polymerized ionic liquids are investigated using broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, and neutron as well as x-ray scattering techniques. The dielectric spectra are dominated on the low frequency regime by electrode polarization while hopping conduction is the underlying mechanism at higher frequencies. At their respective calorimetric glass transition temperatures, a strong correlation between the morphology and ionic conductivity is found. These results are discussed within the recent approaches proposed to explain the decoupling of charge transport from structural dynamics. UT/ORNL Science Alliance.

  12. Dynamics and structure of room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Fayer, Michael D.

    2014-11-01

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

  13. Stability of polypyrrole soft actuators in ionic liquids

    NASA Astrophysics Data System (ADS)

    Kaneto, Keiicgi; Takashima, Wataru

    2012-04-01

    Characteristics of electrochemomechanical deformation (ECMD) of polypyrrole films using ionic liquids are reported. The PPy film prepared by electrodeposition in an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluorometylsulfonyl)imide, BMPTFSI) was compact and high density. The other film prepared from LiTSFI/methyl benzoate and dimethyl phthalate mixed solvents was porous and low density. Both films demonstrated a stable ECMD in the ionic liquid. The strain of ECMD was 3-5% and superimposed on a creeping, showing a typical behaviour of cation movement. The Strains of ECMD in both films operated in a mixed electrolyte of BMPTFSI and propylene carbonate were enhanced up to 17- 25 %, showing anion movement. However, the large strain decreased upon several electrochemical cycles. The results were discussed in terms of swelling of the PPy film by solvents and loss of electrochemical activity.

  14. Methods for separating medical isotopes using ionic liquids

    DOEpatents

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

    2014-10-21

    A method for extracting a radioisotope from an aqueous solution, the method comprising: a) intimately mixing a non-chelating ionic liquid with the aqueous solution to transfer at least a portion of said radioisotope to said non-chelating ionic liquid; and b) separating the non-chelating ionic liquid from the aqueous solution. In preferred embodiments, the method achieves an extraction efficiency of at least 80%, or a separation factor of at least 1.times.10.sup.4 when more than one radioisotope is included in the aqueous solution. In particular embodiments, the method is applied to the separation of medical isotopes pairs, such as Th from Ac (Th-229/Ac-225, Ac-227/Th-227), or Ra from Ac (Ac-225 and Ra-225, Ac-227 and Ra-223), or Ra from Th (Th-227 and Ra-223, Th-229 and Ra-225).

  15. Tuning the Carbon Dioxide Absorption in Amino Acid Ionic Liquids.

    PubMed

    Firaha, Dzmitry S; Kirchner, Barbara

    2016-07-01

    One of the possible solutions to prevent global climate change is the reduction of CO2 emissions, which is highly desired for the sustainable development of our society. In this work, the chemical absorption of carbon dioxide in amino acid ionic liquids was studied through first-principles methods. The use of readily accessible and biodegradable amino acids as building blocks for ionic liquids makes them highly promising replacements for the widely applied hazardous aqueous solutions of amines. A detailed insight into the reaction mechanism of the CO2 absorption was obtained through state-of-the-art theoretical methods. This allowed us to determine the reason for the specific CO2 capacities found experimentally. Moreover, we have also conducted a theoretical design of ionic liquids to provide valuable insights into the precise tuning of the energetic and kinetic parameters of the CO2 absorption. PMID:27214652

  16. Thermophysical properties of phosphonium-based ionic liquids

    PubMed Central

    Bhattacharjee, Arijit; Lopes-da-Silva, José A.; Freire, Mara G.; Coutinho, João A. P.; Carvalho, Pedro J.

    2015-01-01

    Experimental data for density, viscosity, refractive index and surface tension of four phosphonium-based ionic liquids were measured in the temperature range between (288.15 and 353.15) K and at atmospheric pressure. The ionic liquids considered include tri(isobutyl) methylphosphonium tosylate, [Pi(444)1][Tos], tri(butyl)methylphosphonium methylsulfate, [P4441][CH3SO4], tri(butyl)ethylphosphonium diethylphosphate, [P4442][(C2H5O)2PO2], and tetraoctylphosphonium bromide, [P8888][Br]. Additionally, derivative properties, such as the isobaric thermal expansion coefficient, the surface thermodynamic properties and the critical temperatures for the investigated ionic liquids were also estimated and are presented and discussed. Group contribution methods were evaluated and fitted to the density, viscosity and refractive index experimental data. PMID:26435574

  17. Novel 2-alkyl-1-ethylpyridinium ionic liquids: synthesis, dissociation energies and volatility.

    PubMed

    Vilas, Miguel; Rocha, Marisa A A; Fernandes, Ana M; Tojo, Emilia; Santos, Luís M N B F

    2015-01-28

    This work presents the synthesis, volatility study and electrospray ionization mass spectrometry with energy-variable collision induced dissociation of the isolated [(cation)2(anion)](+) of a novel series of 2-alkyl-1-ethyl pyridinium based ionic liquids, [(2)CN-2(1)C2Py][NTf2]. Compared to the imidazolium based ionic liquids, the new ionic liquid series presents a higher thermal stability and lower volatility. The [(cation)2(anion)](+) collision induced dissociation energies of both [(2)CN-2(1)C2Py][NTf2] and [CNPy][NTf2] pyridinium series show an identical trend with a pronounced decrease of the relative cation-anion interaction energy towards an almost constant value for N = 6. It was found that the lower volatility of [(2)CN-2(1)C2Py][NTf2] with a shorter alkyl chain length is due to its higher enthalpy of vaporization. Starting from [(2)C3(1)C2Py][NTf2], the lower volatility is governed by the combination of slightly lower entropies and higher enthalpies of vaporization, an indication of a higher structural disorder of the pyridinium based ionic liquids than the imidazolium based ionic liquids. Dissociation energies and volatility trends support the cohesive energy interpretation model based on the overlapping of the electrostatic and van der Waals functional interaction potentials. PMID:25493639

  18. Structural studies of ionic liquid-modified microemulsions.

    PubMed

    Rojas, Oscar; Koetz, Joachim; Kosmella, Sabine; Tiersch, Brigitte; Wacker, Philipp; Kramer, Markus

    2009-05-15

    This work is focused on the influence of an ionic liquid (IL), i.e. ethyl-methylimidazolium hexylsulfate, on the spontaneous formation of microemulsions with ionic surfactants. The influence of the ionic liquid on structure formation in the optically clear phase region in water/toluene/pentanol mixtures in presence of the cationic surfactant CTAB was studied in more detail. The results show a significant increase of the transparent phase region by adding the ionic liquid. Conductometric investigations demonstrate that adding the ionic liquid can drastically reduce the droplet-droplet interactions in the L(2) phase. (1)H nuclear magnetic resonance ((1)H NMR) diffusion coefficient measurements in combination with dynamic light scattering measurements clearly show that inverse microemulsion droplets still exist, but the droplet size is decreased to 2 nm. A more detailed characterisation of the isotropic phase channel by means of conductivity measurements, dynamic light scattering (DLS), (1)H NMR and cryo-scanning electron microscopy (SEM), allows the identification of a bicontinuous sponge phase between the L(1) and L(2) phase. When the poly(ethyleneimine) is added, the isotropic phase range is reduced drastically, but the inverse microemulsion range still exists. PMID:19278685

  19. Evaluation of cation-anion interaction strength in ionic liquids.

    PubMed

    Fernandes, Ana M; Rocha, Marisa A A; Freire, Mara G; Marrucho, Isabel M; Coutinho, João A P; Santos, Luís M N B F

    2011-04-14

    Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry. PMID:21425809

  20. Diphosphonium Ionic Liquids as Broad Spectrum Antimicrobial Agents

    PubMed Central

    O’Toole, George A.; Wathier, Michel; Zegans, Michael E.; Shanks, Robert M.Q.; Kowalski, Regis; Grinstaff, Mark W.

    2011-01-01

    Purpose One of the most disturbing trends in recent years is the growth of resistant strains of bacteria with the simultaneous dearth of new antimicrobial agents. Thus, new antimicrobial agents for use on the ocular surface are needed. Methods We synthesized a variety of ionic liquid compounds, which possess two positively charged phosphonium groups separated by ten methylene units in a “bola” type configuration. We tested these compounds for antimicrobial activity versus a variety of ocular pathogens, as well as their cytoxicity in vitro in a corneal cell line and in vivo in mice. Results The ionic liquid Di-Hex C10 demonstrated broad in vitro antimicrobial activity at the low micromolar concentrations versus Gram-negative and Gram-positive organisms, including methicillin-resistant Staphylococcus aureus strains, as well as ocular fungal pathogens. Treatment with Di-Hex C10 resulted in bacterial killing in as little as 15 minutes in vitro. Di-Hex C10 showed little cytotoxicity at 1 μM versus a corneal epithelial cell line or at 10 μM in a mouse corneal wound model. We also show that this bis-phosphonium ionic liquid structure is key, as a comparable mono phosphonium ionic liquid is cytotoxic to both bacteria and corneal epithelial cells. Conclusions Here we report the first use of dicationic bis-phosphonium ionic liquids as antimicrobial agents. Our data suggest that diphosphonium ionic liquids may represent a new class of broad-spectrum antimicrobial agents for use on the ocular surface. PMID:22236790

  1. 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

  2. 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

  3. Ionic liquids: the link to high-temperature molten salts?

    PubMed

    El Abedin, Sherif Zein; Endres, Frank

    2007-11-01

    Due to their wide thermal windows, ionic liquids can be regarded as the missing link between aqueous/organic solutions and high-temperature molten salts. They can be employed efficiently for the coating of other metals with thin layers of tantalum, aluminum, and presumably many others at reasonable temperatures by electrochemical means. The development of ionic liquids, especially air and water stable ones, has opened the door for the electrodeposition of reactive elements such as, for example, Al, Ta, and Si, which in the past were only accessible using high-temperature molten salts or, in part, organic solvents. PMID:17521159

  4. The evaporation study of silicon-containing ionic liquid

    NASA Astrophysics Data System (ADS)

    Chilingarov, Norbert S.; Medvedev, Artem A.; Deyko, Grigoriy S.; Kustov, Leonid M.; Chernikova, Elena A.; Glukhov, Lev M.; Polyakova, Marina V.; Ioutsi, Vitaliy A.; Markov, Vitaliy Yu.; Sidorov, Lev N.

    2016-07-01

    1,2-Dimethyl-3-(1‧,1‧,3‧,3‧-tetramethyl-3‧-phenyldisiloxanyl)methylimidazolium bis(trifluoromethanesulfonyl)amide ([PhC5OSi2MMIm+][Tf2N-]) is the first silicon-containing ionic liquid which was characterized with the vaporization enthalpy, (138.5 ± 1.8) kJ mol-1, and saturated vapor pressure, ln(p/Pa) = -(16656 ± 219)/(T/K) + (30.69 ± 0.92). This compound is a unique ionic liquid giving ions, retaining both cationic and anionic portions, in the electron impact ionization (EI) mass spectrum.

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

    SciTech Connect

    Reddy, Ramana

    2009-01-31

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

  6. 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

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

    SciTech Connect

    Reddy, Ramana G

    2009-01-31

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

  8. Tuning the ionic conductivity in protic polymerized ionic liquid homo, random, and block copolymers

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Segalman, Rachel; UCSB Team

    2015-03-01

    Proton conducting membranes are of interest for a number of energy applications including use in fuel cells and artificial photosynthesis systems. We have synthesized a new class of protic polymerized ionic liquids (PILs) based on imidazolium cations which exhibit high conductivities in the solid state. In contrast to previous imidazolium based PILs, the ionic liquid moiety is attached via a carbon on the imidazole thus leaving the two nitrogens available to act as a proton donor/acceptor. The conductivies of these protic PILs, measured by dielectric spectroscopy, are orders of magnitude higher than the analogous non-protic PILs at a given distance above (Tg). These high conductivities are the result of a strong contribution from proton motion. A series of random and block copolymers containing the polymerized ionic liquid monomer and a non-ionic comonomer were also investigated to determine the role of comonomer on the conductivity of these materials. It was found that methyl acrylate, which has a low glass transition temperature and high dielectric constant, can result in improvements of ionic conductivity. Studies using solid state NMR are underway to understand the role of protons and mobile anions in controlling the overall conductivity of these materials.

  9. Supported liquid membrane electrochemical separators

    SciTech Connect

    Pemsler, J. Paul; Dempsey, Michael D.

    1986-01-01

    Supported liquid membrane separators improve the flexibility, efficiency and service life of electrochemical cells for a variety of applications. In the field of electrochemical storage, an alkaline secondary battery with improved service life is described in which a supported liquid membrane is interposed between the positive and negative electrodes. The supported liquid membranes of this invention can be used in energy production and storage systems, electrosynthesis systems, and in systems for the electrowinning and electrorefining of metals.

  10. Charge Transport and Glassy Dynamics in Ionic Liquids

    SciTech Connect

    Sangoro, Joshua R; Kremer, Friedrich

    2012-01-01

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on EinsteinSmoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids.

  11. Charge transport and glassy dynamics in ionic liquids.

    PubMed

    Sangoro, Joshua R; Kremer, Friedrich

    2012-04-17

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on Einstein-Smoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids. PMID:22082024

  12. 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

  13. Blending ionic liquids: how physico-chemical properties change.

    PubMed

    Castiglione, Franca; Raos, Guido; Appetecchi, Giovanni Battista; Montanino, Maria; Passerini, Stefano; Moreno, Margherita; Famulari, Antonino; Mele, Andrea

    2010-02-28

    Ionic liquids offer the opportunity of tailoring their properties by changing the chemical structure of the cation and anion. Blending of two or more liquids adds a further dimension to this "chemical space". Here we present the results of a study of three binary and one ternary mixture of the ionic liquids formed by the N-butyl-N-methylpyrrolidinium cation with bis(trifluoromethanesulfonyl) imide, bis(pentafluoroethanesulfonyl) imide and (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl) imide. We have collected viscosity and NMR-based data on ionxion correlations (NOE) and diffusion (DOSY). We also attempt to establish a quantitative correlation between mixture and the corresponding pure liquid properties. We find that the binary mixture containing the two very different anions has an intriguing and somewhat anomalous behaviour. PMID:20145843

  14. Synthesis and characterization of ionic liquid (EMImBF4)/Li+ - chitosan membranes for ion battery

    NASA Astrophysics Data System (ADS)

    Pasaribu, Marvin H.; Arcana, I. Made; Wahyuningrum, Deana

    2015-09-01

    Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li+ ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anion metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10-2 S cm- 1 for chitosan to 1.30 × 10-2 S cm-1 for chitosan with EMImBF4/Li+, and this result was supported by analysis the surface morphology (SEM).

  15. Ionic liquids as potential carriers of low viscosity magnetorheological fluids

    NASA Astrophysics Data System (ADS)

    Guerrero-Sanchez, Carlos; Ortiz-Alvarado, Armando; Schubert, Ulrich S.

    2009-03-01

    Based on the latest investigations on the formulation of new magneto-rheological fluids, it is envisioned that the use of ionic liquids as carriers of magneto-rheological fluids will open new possibilities of applications for these smart fluids due to the fact that their physical and chemical properties can be fine-tuned in a broad range. This contribution addresses one potentially important advantage of magneto-rheological fluids which use ionic liquids as novel carriers. In connection with this, magneto-rheological fluids with a low viscosity in the off-state without compromising other properties of the formulations (e. g., sedimentation of the dispersed magnetic particles, liquid state of the carriers in a broad range of temperatures) are often required for specific applications. In this regard, ionic liquids of low viscosity can be very useful in the development of such magneto-rheological fluids. Thus, this contribution reports on the magnetorheological properties of iron(II, III) oxide particles dispersed in the ionic liquid 1-ethyl-3-methylimidazolium thiocyanate (a low viscosity ionic liquid) in the temperature range from 20 °C to 80 °C. The experimental results have revealed that the apparent viscosity of the dispersion slightly changes with the temperature when a constant magnetic field is applied and its value mainly depends on the shear rate and the strength of the magnetic field. The viscosity of the dispersion remains practically unmodified with both the temperature and the magnetic field intensity as the magnetic saturation of the material is reached; in this regime the viscosity will only depend on the applied shear rate. In contrast, the yield stress values of the dispersion as well as the corresponding shear stress vs. shear rate curves have shown an inverse behavior with temperature for a constant magnetic field.

  16. Benzene solubility in ionic liquids: working toward an understanding of liquid clathrate formation.

    PubMed

    Pereira, Jorge F B; Flores, Luis A; Wang, Hui; Rogers, Robin D

    2014-11-17

    The solubility of benzene in 15 imidazolium, pyrrolidinium, pyridinium, and piperidinium ionic liquids has been determined; the resulting, benzene-saturated ionic liquid solutions, also known as liquid clathrates, were examined with (1) H and (19) F nuclear magnetic resonance spectroscopy to try and understand the molecular interactions that control liquid clathrate formation. The results suggest that benzene interacts primarily with the cation of the ionic liquid, and that liquid clathrate formation (and benzene solubility) is controlled by the strength of the cation-anion interactions, that is, the stronger the cation-anion interaction, the lower the benzene solubility. Other factors that were determined to be important in the final amount of benzene in any given liquid clathrate phase included attractive interactions between the anion and benzene (when significant), and larger steric or free volume demands of the ions, both of which lead to greater benzene solubility. PMID:25297708

  17. Ionic liquid-facilitated preparation of lignocellulosic composites

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lignocellulosic composites (LCs) were prepared by partially dissolving cotton along with steam exploded Aspen wood and burlap fabric reinforcements utilizing an ionic liquid (IL) solvent. Two methods of preparation were employed. In the first method, a controlled amount of IL was added to preassembl...

  18. EVALUATING THE GREENNESS OF IONIC LIQUIDS VIA LIFE CYCLE ASSESSMENT

    EPA Science Inventory

    Ionic Liquids have been suggested as "greener" replacements to traditional solvents. However, the environmental impacts of the life cycle phases have not been studied. Such a "cradle to gate" Life Cycle Assessment (LCA) for comparing the environmental impact of various solvents...

  19. Lunar Oxygen Production and Metals Extraction Using Ionic Liquids

    NASA Technical Reports Server (NTRS)

    Marone, Matthew; Paley, Mark Steven; Donovan, David N.; Karr, Laurel J.

    2009-01-01

    Initial results indicate that ionic liquids are promising media for the extraction of oxygen from lunar regolith. IL acid systems can solubilize regolith and produce water with high efficiency. IL electrolytes are effective for water electrolysis, and the spent IL acid media are capable of regeneration.

  20. SOLVENT-FREE SONOCHEMICAL PREPARATION OF IONIC LIQUIDS

    EPA Science Inventory

    An ultrasound-assisted preparation of a series of ambient temperature ionic liquids, 1-alkyl-3-methylimidazolium (AMIM) halides, that proceeds via efficient reaction of 1-methyl imidazole with alkyl halides/terminal dihalides under solvent-free conditions, is described.

  1. Thermoelectric Power in Bilayer Graphene Device with Ionic Liquid Gating

    NASA Astrophysics Data System (ADS)

    Chien, Yung-Yu; Yuan, Hongtao; Wang, Chang-Ran; Lee, Wei-Li

    2016-02-01

    The quest for materials showing large thermoelectric power has long been one of the important subjects in material science and technology. Such materials have great potential for thermoelectric cooling and also high figure of merit ZT thermoelectric applications. We have fabricated bilayer graphene devices with ionic-liquid gating in order to tune its band gap via application of a perpendicular electric field on a bilayer graphene. By keeping the Fermi level at charge neutral point during the cool-down, we found that the charge puddles effect can be greatly reduced and thus largely improve the transport properties at low T in graphene-based devices using ionic liquid gating. At (Vig, Vbg) = (-1 V, +23 V), a band gap of about 36.6 ± 3 meV forms, and a nearly 40% enhancement of thermoelectric power at T = 120 K is clearly observed. Our works demonstrate the feasibility of band gap tuning in a bilayer graphene using ionic liquid gating. We also remark on the significant influence of the charge puddles effect in ionic-liquid-based devices.

  2. 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.

  3. Carbon Dioxide Capture by Superbase-Derived Protic Ionic Liquids

    SciTech Connect

    Dai, Sheng; Luo, Huimin; Li, Haoran; Wang, Chongmin; Jiang, Deen

    2010-01-01

    Protic ionic liquids (PILs) from a superbase and fluorinated alcohol, imidazole, pyrrolinone, or phenol were designed to capture CO{sub 2} based on the reactivity of their anions to CO{sub 2}. These PILs are capable of rapid and reversible capture of about one equivalent of CO{sub 2}, which is superior to those sorption systems based on traditional aprotic ILs.

  4. Inhibited fragmentation of mAbs in buffered ionic liquids.

    PubMed

    Mazid, Romiza R; Vijayaraghavan, R; MacFarlane, Douglas R; Cortez-Jugo, Christina; Cheng, Wenlong

    2015-05-11

    We thoroughly investigated the biological, structural and chemical stability of epidermal growth factor receptor monoclonal antibody (EGFR mAb) using choline-based buffered ionic liquids (BILs). The results demonstrated substantially enhanced stabilities in our BILs, indicating their huge promise as real-world green biological buffers for antibody storage and transportation. PMID:25869239

  5. Molecular dynamics simulations of ionic liquid nanodroplets in electric fields

    NASA Astrophysics Data System (ADS)

    Tiruppathi, Pavithra C.

    2011-12-01

    Ionic liquids are appropriate for the application of electrospray thruster propulsion due to their physical properties such as low volatility and high electrical conductivity. The behavior of ionic liquid droplets and resulting ion and cluster emission in the presence of an electric field impacts the efficiency and thrust of the electrospray thruster. The technique of molecular simulation allows for the study of ionic liquid nanodroplets in atomic detail which is a limitation in mass spectrometric experiments. This thesis discusses the investigation of nanodroplets of the ionic liquid 1-ethyl-3- methylimidaziolium bis(triuoromethylsulfonyl)imide ([Emim+][Tf2n -]) in the presence of an electric field using molecular dynamics simulations. The ratio of the single ions to large clusters emitted from the droplet are observed and compared with experiment. The critical field strength required for ion emission from the droplet agrees with experiment. The critical field strength is also computed as a function of droplet size. The thermal stabilities, structural and dynamical properties are analyzed for the ([Emim +][Tf2n-]) nanodroplets.

  6. Hydrolysis of cellulose catalyzed by novel acidic ionic liquids.

    PubMed

    Zhuo, Kelei; Du, Quanzhou; Bai, Guangyue; Wang, Congyue; Chen, Yujuan; Wang, Jianji

    2015-01-22

    The conversion of cellulosic biomass directly into valuable chemicals becomes a hot subject. Six novel acidic ionic liquids (ILs) based on 2-phenyl-2-imidazoline were synthesized and characterized by UV-VIS, TGA, and NMR. The novel acidic ionic liquids were investigated as catalysts for the hydrolysis of cellulose in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). The acidic ionic liquids with anions HSO4(-) and Cl(-) showed better catalytic performance for the hydrolysis of cellulose than those with H2PO4(-). The temperature and dosage of water affect significantly the yield of total reducing sugar (TRS). When the hydrolysis of cellulose was catalyzed by 1-propyl sulfonic acid-2-phenyl imidazoline hydrogensulfate (IL-1) and the dosage of water was 0.2g, the TRS yield was up to 85.1% within 60 min at 100°C. These new acidic ionic liquids catalysts are expected to have a wide application in the conversion of cellulose into valuable chemicals. PMID:25439867

  7. EXPEDITIOUS SOLVENT-FREE PREPARATION OF IONIC LIQUIDS USING MICROWAVES

    EPA Science Inventory

    Ambient temperature ionic liquids comprising 1,3-dialkylimidazolium cations have shown great promise as alternative solvents in view of their negligible vapor pressure, ease of handling and potential for recycling. An efficient solventless protocol for the preparation of a wide v...

  8. Thermal decomposition of carboxylate ionic liquids: trends and mechanisms.

    PubMed

    Clough, Matthew T; Geyer, Karolin; Hunt, Patricia A; Mertes, Jürgen; Welton, Tom

    2013-12-21

    The thermal stability of a series of dialkylimidazolium carboxylate ionic liquids has been investigated using a broad range of experimental and computational techniques. Ionic liquids incorporating fluoroalkyl carboxylate anions were found to have profoundly differing thermal stabilities and decomposition mechanisms compared with their non-fluorinated analogues. 1-Ethyl-3-methylimidazolium acetate was observed to largely decompose via an S(N)2 nucleophilic substitution reaction when under inert gas conditions, predominantly at the imidazolium methyl substituent. The Arrhenius equations for thermal decomposition of 1-ethyl-3-methylimidazolium acetate, and the C(2)-methylated analogue 1-ethyl-2,3-dimethylimidazolium acetate, were determined from isothermal Thermogravimetric Analysis experiments. The low thermal stability of 1-ethyl-3-methylimidazolium acetate has important implications for biomass experiments employing this ionic liquid. For these two ionic liquids, ion pair and transition state structures were optimised using Density Functional Theory. The activation barriers for the S(N)2 nucleophilic substitution mechanisms are in good agreement with the experimentally determined values. PMID:24173605

  9. How can a carbene be active in an ionic liquid?

    PubMed

    Thomas, Martin; Brehm, Martin; Hollóczki, Oldamur; Kirchner, Barbara

    2014-02-01

    The solvation of the carbene 1-ethyl-3-methylimidazole-2-ylidene in the ionic liquid 1-ethyl-3-methylimidazolium acetate was investigated by ab initio molecular dynamics simulations in order to reveal the interaction between these two highly important classes of materials: N-heterocyclic carbenes with superb catalytic activity and ionic liquids with advantageous properties as solvents and reaction media. In contrast to previously published data on analogous systems, no hydrogen bond is observed between the hypovalent carbon atom and the most acidic ring hydrogen atoms, as these interaction sites of the imidazolium ring are predominantly occupied by the acetate ions. Keeping the carbene away from the ring hydrogen atoms prevents stabilization of this reactive species, and hence any retarding effect on subsequent reactions, which explains the observed high reactivity of the carbene in acetate-based ionic liquids. Instead, the carbene exhibits a weaker interaction with the methyl group of the imidazolium cation by forming a hitherto unprecedented kind of C⋅⋅⋅H-C hydrogen bond. This unexpected finding not only indicates a novel kind of hydrogen bond for carbenes, but also shows that such interaction sites of the imidazolium cation are not limited to the ring hydrogen atoms. Thus, the results give the solute-solvent interactions within ionic liquids a new perspective, and provide a further, albeit weak, site of interaction to tune in order to achieve the desired environment for any dissolved active ingredient. PMID:24375892

  10. Biodegradation of imidazolium ionic liquids by activated sludge microorganisms.

    PubMed

    Liwarska-Bizukojc, Ewa; Maton, Cedric; Stevens, Christian V

    2015-11-01

    Biological properties of ionic liquids (ILs) have been usually tested with the help of standard biodegradation or ecotoxicity tests. So far, several articles on the identification of intermediate metabolites of microbiological decay of ILs have been published. Simultaneously, the number of novel ILs with unrecognized characteristics regarding biodegradability and effect on organisms and environment is still increasing. In this work, seven imidazolium ionic liquids of different chemical structure were studied. Three of them are 1-alkyl-3-methyl-imidazolium bromides, while the other four are tetra- or completely substituted imidazolium iodides. This study focused on the identification of intermediate metabolites of the aforementioned ionic liquids subjected to biodegradation in a laboratory activated sludge system. Both fully substituted ionic liquids and 1-ethyl-3-methyl-imidazolium bromide were barely biodegradable. In the case of two of them, no biotransformation products were detected. The elongation of the alkyl side chain made the IL more susceptible for microbiological decomposition. 1-Decyl-3-methyl-imidazolium bromide was biotransformed most easily. Its primary biodegradation up to 100 % could be achieved. Nevertheless, the cleavage of the imidazolium ring has not been observed. PMID:26463469

  11. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    EPA Science Inventory

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  12. High performance batteries with carbon nanomaterials and ionic liquids

    DOEpatents

    Lu, Wen

    2012-08-07

    The present invention is directed to lithium-ion batteries in general and more particularly to lithium-ion batteries based on aligned graphene ribbon anodes, V.sub.2O.sub.5 graphene ribbon composite cathodes, and ionic liquid electrolytes. The lithium-ion batteries have excellent performance metrics of cell voltages, energy densities, and power densities.

  13. Recent Developments in Chemical Synthesis with Biocatalysts in Ionic Liquids.

    PubMed

    Potdar, Mahesh K; Kelso, Geoffrey F; Schwarz, Lachlan; Zhang, Chunfang; Hearn, Milton T W

    2015-01-01

    Over the past decade, a variety of ionic liquids have emerged as greener solvents for use in the chemical manufacturing industries. Their unique properties have attracted the interest of chemists worldwide to employ them as replacement for conventional solvents in a diverse range of chemical transformations including biotransformations. Biocatalysts are often regarded as green catalysts compared to conventional chemical catalysts in organic synthesis owing to their properties of low toxicity, biodegradability, excellent selectivity and good catalytic performance under mild reaction conditions. Similarly, a selected number of specific ionic liquids can be considered as greener solvents superior to organic solvents owing to their negligible vapor pressure, low flammability, low toxicity and ability to dissolve a wide range of organic and biological substances, including proteins. A combination of biocatalysts and ionic liquids thus appears to be a logical and promising opportunity for industrial use as an alternative to conventional organic chemistry processes employing organic solvents. This article provides an overview of recent developments in this field with special emphasis on the application of more sustainable enzyme-catalyzed reactions and separation processes employing ionic liquids, driven by advances in fundamental knowledge, process optimization and industrial deployment. PMID:26389873

  14. High performance ultracapacitors with carbon nanomaterials and ionic liquids

    DOEpatents

    Lu, Wen; Henry, Kent Douglas

    2012-10-09

    The present invention is directed to the use of carbon nanotubes and/or electrolyte structures in various electrochemical devices, such as ultracapacitors having an ionic liquid electrolyte. The carbon nanotubes are preferably aligned carbon nanotubes. Compared to randomly entangled carbon nanotubes, aligned carbon nanotubes can have better defined pore structures and higher specific surface areas.

  15. Mixing Enthalpy for Binary Mixtures Containing Ionic Liquids.

    PubMed

    Podgoršek, A; Jacquemin, J; Pádua, A A H; Costa Gomes, M F

    2016-05-25

    A complete review of the published data on the mixing enthalpies of mixtures containing ionic liquids, measured directly using calorimetric techniques, is presented in this paper. The field of ionic liquids is very active and a number of research groups in the world are dealing with different applications of these fluids in the fields of chemistry, chemical engineering, energy, gas storage and separation or materials science. In all these fields, the knowledge of the energetics of mixing is capital both to understand the interactions between these fluids and the different substrates and also to establish the energy and environmental cost of possible applications. Due to the relative novelty of the field, the published data is sometimes controversial and recent reviews are fragmentary and do not represent a set of reliable data. This fact can be attributed to different reasons: (i) difficulties in controlling the purity and stability of the ionic liquid samples; (ii) availability of accurate experimental techniques, appropriate for the measurement of viscous, charged, complex fluids; and (iii) choice of an appropriate clear thermodynamic formalism to be used by an interdisciplinary scientific community. In this paper, we address all these points and propose a critical review of the published data, advise on the most appropriate apparatus and experimental procedure to measure this type of physical-chemical data in ionic liquids as well as the way to treat the information obtained by an appropriate thermodynamic formalism. PMID:27144455

  16. 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.

  17. Thermoelectric Power in Bilayer Graphene Device with Ionic Liquid Gating

    PubMed Central

    Chien, Yung-Yu; Yuan, Hongtao; Wang, Chang-Ran; Lee, Wei-Li

    2016-01-01

    The quest for materials showing large thermoelectric power has long been one of the important subjects in material science and technology. Such materials have great potential for thermoelectric cooling and also high figure of merit ZT thermoelectric applications. We have fabricated bilayer graphene devices with ionic-liquid gating in order to tune its band gap via application of a perpendicular electric field on a bilayer graphene. By keeping the Fermi level at charge neutral point during the cool-down, we found that the charge puddles effect can be greatly reduced and thus largely improve the transport properties at low T in graphene-based devices using ionic liquid gating. At (Vig, Vbg) = (−1 V, +23 V), a band gap of about 36.6 ± 3 meV forms, and a nearly 40% enhancement of thermoelectric power at T = 120 K is clearly observed. Our works demonstrate the feasibility of band gap tuning in a bilayer graphene using ionic liquid gating. We also remark on the significant influence of the charge puddles effect in ionic-liquid-based devices. PMID:26852799

  18. Method for synthesis of titanium dioxide nanotubes using ionic liquids

    SciTech Connect

    Qu, Jun; Luo, Huimin; Dai, Sheng

    2013-11-19

    The invention is directed to a method for producing titanium dioxide nanotubes, the method comprising anodizing titanium metal in contact with an electrolytic medium containing an ionic liquid. The invention is also directed to the resulting titanium dioxide nanotubes, as well as devices incorporating the nanotubes, such as photovoltaic devices, hydrogen generation devices, and hydrogen detection devices.

  19. Formation of a liquid-crystalline interpenetrating poly-(ionic liquid) network hydrogel.

    SciTech Connect

    Becht, G. A.; Sofos, M.; Seifert, S.; Firestone, M. A.

    2011-02-21

    Preparation of a liquid-crystalline ionic-liquid (IL)-based interpenetrating polymer network (IPN) is described. The IPN is prepared sequentially by first photopolymerizing a self-assembled aqueous mixture of an IL monomer (1-(10-(acryloyloxy)decyl)-3-methylimidazolium chloride) that possesses an acryloyl moiety at the terminus of a C{sub 10} alkyl chain of the IL cation. In the second step, an acrylate counteranion is introduced and then photopolymerized to yield a durable self-supporting network polymer. Thermal analysis indicates the formation of a homogeneous (well-blended constituent polymers) IPN. The IPN adopts a lamellar structure possessing some residual in-plane tetragonal perforations, as evidenced by small-angle X-ray scattering (SAXS). The IPN can absorb large quantities of water, swelling to nearly 60 times its original volume, but retains mechanical integrity making it a durable hydrogel.

  20. DESIGN AND EVALUATION OF IONIC LIQUIDS AS NOVEL CO2 ABSORBENTS

    SciTech Connect

    Edward J. Maginn

    2005-01-31

    Progress from the second quarter of activity on the project ''Design and Evaluation of Ionic Liquids as Novel CO2 Absorbents'' is provided. Major activities in three areas are reported: ''compound synthesis, property measurement and molecular modeling''. Two new ionic liquid compounds have been synthesized and characterized. Viscosities, densities and gas solubilities have been measured for several of the ionic liquids synthesized during Q1. Continued progress on computational modeling of the ionic liquids has been made.

  1. Effect of Electric Field Alignment on Morphology and Ionic Conductivity of Polymerized Ionic Liquid Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Nykaza, Jacob; Elabd, Yossef A.; Winey, Karen I.

    2014-03-01

    Polymerized ionic liquid (PIL) block copolymers are appealing for numerous electrochemical applications, including solid polymer electrolyte membranes for batteries and anion exchange membranes for fuel cells. The extent to which the reduced segmental motion caused by the non-conducting polymer segments and grain boundaries between block copolymer microdomains are detrimental to ionic conductivity is unknown. Increased long-range morphological order and connectivity of PIL microdomains are key to understanding the ion transport mechanism and may improve the ionic conductivity of PIL block copolymers. The effect of electric field on the morphology and ionic conductivity of poly(styrene- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-bis(trifluoromethanesulfonyl)imide)) (PS- b-PMEBIm-TFSI) will be discussed as a function of microdomain orientation. Electric field is used to increase the perpendicular orientation of ion-conducting pathways with respect to the electrodes. The morphology and ionic conductivity were characterized by small-angle X-ray scattering and electrochemical impedance spectroscopy, respectively. The ionic conductivity of unoriented and oriented block copolymers will be compared to the PIL homopolymer, PMEBIm-TFSI, using the Sax and Ottino model.

  2. Electrolytic Conductivity of Four Imidazolium-Based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Calado, Marta S.; Diogo, João C. F.; Correia da Mata, José L.; Caetano, Fernando J. P.; Visak, Zoran P.; Fareleira, João M. N. A.

    2013-07-01

    In this article, electrolytic (ionic) conductivity measurements of four ionic liquids (ILs), namely, 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ([Cmim][NTf]), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Cmim][OTf]), 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Cmim][NTf]), and 1-ethyl-3-methylimidazolium ethyl sulfate ([Cmim][EtSO]) (ECOENG212), were performed in a temperature range of (288.15 to 333.15) K. [Cmim][NTf] was chosen to be a reference ionic liquid for several properties, including the electrolytic conductivity by the IUPAC Project 2002-005-1-100. For that reason, the measurements performed with that ionic liquid primarily serve the purpose to validate the instrumentation and the experimental procedure used in this work. The measurements were carried out using a complex impedance method, applying a novel electronic device designed and constructed for this purpose. The complete setup includes a Schott Instruments LF 913 T, used as a four-electrode conductivity cell, and a lock-in amplifier. The cell was calibrated using standard reference KCl aqueous solutions. The measurements of the impedance of the conductivity cell were carried out along a range of frequencies from (0.2 to 30) kHz, and the results were extrapolated to infinite frequency, in order to determine the electrolytic conductivity of the liquid samples. The results obtained for the ionic liquid [Cmim][NTf] were compared to reference data, and it was estimated that the overall uncertainty of the present results is better than 2 %. All the data obtained were compared with available literature data, and were analyzed and discussed in respect to the effect of temperature, cation alkyl chain length, and anion.

  3. 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.

  4. Solvent extraction of rare-earth ions based on functionalized ionic liquids

    SciTech Connect

    Sun, Xiaoqi; Dai, Sheng; Luo, Huimin

    2012-01-01

    We herein report the achievement of enhanced extractabilities and selectivities for separation of rare earth elements based on functionalized ionic liquids. This work highlights the potential of developing a comprehensive ionic liquid-based extraction strategy for rare earth elements using ionic liquids as both extractant and diluent.

  5. A NEW CLASS OF SOLVENTS FOR TRU DISSOLUTION AND SEPARATION: IONIC LIQUIDS

    EPA Science Inventory

    This report focuses on the progress of a study of a New Class of Solvents for TRU Dissolution and Separation: Ionic Liquids. Key research issues are: (1) examining Cs, Sr, Tc, and TRU partitioning in Ionic Liquid/aqueous systems; (2) developing new Ionic Liquids for TRU separat...

  6. Vaporisation and thermal decomposition of dialkylimidazolium halide ion ionic liquids.

    PubMed

    Lovelock, Kevin R J; Armstrong, James P; Licence, Peter; Jones, Robert G

    2014-01-28

    Vaporisation and liquid phase thermal decomposition, TD, of two halide ion ionic liquids, 1-octyl-3-methylimidazolium chloride, [C8C1Im]Cl, and 1-octyl-3-methylimidazolium iodide, [C8C1Im]I, are investigated using temperature programmed desorption (TPD) line of sight mass spectrometry (LOSMS) at ultra-high vacuum (UHV). The ability to use MS to distinguish between vaporisation and TD allows the thermodynamics/kinetics of both vaporisation and TD to be investigated within the same experiments. Vaporisation of both halide ion ionic liquids is demonstrated. For both [C8C1Im]Cl and [C8C1Im]I the vapour is shown to be composed of neutral ion pairs (NIPs). The enthalpy of vaporisation at temperature T, ΔvapHT, was experimentally determined as ΔvapH455 = 151 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH480 = 149 ± 8 kJ mol(-1) for [C8C1Im]I. Extrapolation of ΔvapHT to the reference temperature, 298 K, gave ΔvapH298 = 166 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH298 = 167 ± 8 kJ mol(-1) for [C8C1Im]I, higher than most ΔvapH298 values measured to date for other [C8C1Im](+)-containing ionic liquids. In addition, predictions of ΔvapH298 for other halide ion ionic liquids are made. Liquid phase TD is shown to proceed via nucleophilic substitution to give two sets of products: 1-octylimidazole and methylhalide, and 1-methylimidazole and 1-octylhalide. The activation energy of TD at a temperature T, Ea,TD,T, is measured for the nucleophilic substitution of [C8C1Im]I to give methyliodide; Ea,TD,480 = 136 ± 15 kJ mol(-1). Ea,TD,T is measured for the nucleophilic substitution of [C8C1Im]Cl to give methylchloride; Ea,TD,455 = 132 ± 10 kJ mol(-1). The fact that ΔvapHT and Ea,TD,T are the same (within error) for both ionic liquids is commented upon, and conclusions are drawn as to the thermal stability of these ionic liquids. PMID:24105256

  7. Transports of ionic liquids in ionic polymer conductor network composite actuators

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Liu, Sheng; Lin, Junhong; Wang, Dong; Jain, Vaibhav; Montazami, Reza; Heflin, James R.; Li, Jing; Madsen, Louis; Zhang, Q. M.

    2010-04-01

    We investigate the influence of ionic liquids on the electromechanical performance of Ionic Polymer Conductor Network Composite (IPCNC) bending actuators. Two imidazolium ionic liquids (ILs) with one cation, which is 1-ethyl-3- methylimidazolium ([EMI+]), and two different anions, which are tetrafluoroborate ([BF4-]) and trifluoromethanesulfonate ([Tf-]), are chosen for the study. By combining the time domain electric and electromechanical responses, we developed a new model that describes the ion transports in IPCNC actuators. The time constant of excess cation and anion migration in various composite electrodes are deduced: 6s and 25s in RuO2/Nafion; 7.9s and 36.3s in RuO2/Aquivion; 4.8s and 53s in Au/PAH, respectively. NMR is also applied to provide quantitative measures of self-diffusion coefficients independently for IL anions and cations both in pure ILs and in ILs absorved into ionomers. All the results indicate that the motion of cation, in the studied pure ionic liquids, polymer matrix and conductor network composites, is faster than that of anion. Moreover, the CNC morphology is playing a crucial role in determining the ion transport in the porous electrodes.

  8. Force microscopy of layering and friction in an ionic liquid

    NASA Astrophysics Data System (ADS)

    Hoth, Judith; Hausen, Florian; Müser, Martin H.; Bennewitz, Roland

    2014-07-01

    The mechanical properties of the ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4][FAP]) in confinement between a SiOx and a Au(1 1 1) surface are investigated by means of atomic force microscopy (AFM) under electrochemical control. Up to 12 layers of ion pairs can be detected through force measurements while approaching the tip of the AFM to the surface. The particular shape of the force versus distance curve is explained by a model for the interaction between tip, gold surface and ionic liquid, which assumes an exponentially decaying oscillatory force originating from bulk liquid density correlations. Jumps in the tip-sample distance upon approach correspond to jumps of the compliant force sensor between branches of the oscillatory force curve. Frictional force between the laterally moving tip and the surface is detected only after partial penetration of the last double layer between tip and surface.

  9. Force microscopy of layering and friction in an ionic liquid.

    PubMed

    Hoth, Judith; Hausen, Florian; Müser, Martin H; Bennewitz, Roland

    2014-07-16

    The mechanical properties of the ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4][FAP]) in confinement between a SiOx and a Au(1 1 1) surface are investigated by means of atomic force microscopy (AFM) under electrochemical control. Up to 12 layers of ion pairs can be detected through force measurements while approaching the tip of the AFM to the surface. The particular shape of the force versus distance curve is explained by a model for the interaction between tip, gold surface and ionic liquid, which assumes an exponentially decaying oscillatory force originating from bulk liquid density correlations. Jumps in the tip-sample distance upon approach correspond to jumps of the compliant force sensor between branches of the oscillatory force curve. Frictional force between the laterally moving tip and the surface is detected only after partial penetration of the last double layer between tip and surface. PMID:24919549

  10. Pretreatment of rice hulls by ionic liquid dissolution.

    PubMed

    Lynam, Joan G; Reza, M Toufiq; Vasquez, Victor R; Coronella, Charles J

    2012-06-01

    As a highly available waste product, rice hulls could be a starting block in replacing liquid fossil fuels. However, their silica covering can make further use difficult. This preliminary study investigates effects of dissolving rice hulls in the ionic liquids 1-ethyl-3-methylimidazolium acetate (EMIM Ac), 1-hexyl-3-methylimidazolium chloride, (HMIM Cl), and 1-allyl-3-methylimidazolium chloride (AMIM Cl), and what lignocellulosic components can be precipitated from the used ionic liquid with water and ethanol. EMIM Ac dissolution at 110 °C for 8 h was found to completely remove lignin from rice hulls, while ethanol was capable of precipitating lignin out of the used EMIM Ac. With 8h dissolution at 110 °C using HMIM Cl, approximately 20% of the cellulose in the rice hull sample can be precipitated out using water as co-solvent, while more than 60% of the hemicellulose can be precipitated with ethanol. PMID:22446050

  11. Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew; Leo, Donald

    2005-05-01

    Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

  12. Access to pure and highly volatile hydrochalcogenide ionic liquids.

    PubMed

    Finger, L H; Wohde, F; Grigoryev, E I; Hansmann, A-K; Berger, R; Roling, B; Sundermeyer, J

    2015-11-21

    The reaction of methylcarbonate ionic liquids with H2S or H2Se offers a highly selective synthesis of analytically pure, well-defined and soluble hydrosulphide and hydroselenide organic salts of general interest. Among them, imidazolium hydrochalcogenides show an astonishingly high volatility for cation-aprotic ILs, which allows their quantitative sublimation below 100 °C/10(-2) mbar and actually results in ionic single crystal growth from the gas phase. Vaporisation and decomposition characteristics were investigated by isothermal TGA measurements and DFT calculations. PMID:26377144

  13. Gelled Ionic Liquid-Based Membranes: Achieving a 10,000 GPU Permeance for Post-Combustion Carbon Capture with Gelled Ionic Liquid-Based Membranes

    SciTech Connect

    2011-02-02

    IMPACCT Project: Alongside Los Alamos National Laboratory and the Electric Power Research Institute, CU-Boulder is developing a membrane made of a gelled ionic liquid to capture CO2 from the exhaust of coal-fired power plants. The membranes are created by spraying the gelled ionic liquids in thin layers onto porous support structures using a specialized coating technique. The new membrane is highly efficient at pulling CO2 out of coal-derived flue gas exhaust while restricting the flow of other materials through it. The design involves few chemicals or moving parts and is more mechanically stable than current technologies. The team is now working to further optimize the gelled materials for CO2 separation and create a membrane layer that is less than 1 micrometer thick.

  14. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    SciTech Connect

    Wishart,J.F.

    2008-09-29

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate

  15. Can Ionic Liquids Be Used As Templating Agents For Controlled Design of Uranium-Containing Nanomaterials?

    SciTech Connect

    Visser, A.; Bridges, N.; Tosten, M.

    2013-04-09

    Nanostructured uranium oxides have been prepared in ionic liquids as templating agents. Using the ionic liquids as reaction media for inorganic nanomaterials takes advantage of the pre-organized structure of the ionic liquids which in turn controls the morphology of the inorganic nanomaterials. Variation of ionic liquid cation structure was investigated to determine the impact on the uranium oxide morphologies. For two ionic liquid cations, increasing the alkyl chain length increases the aspect ratio of the resulting nanostructured oxides. Understanding the resulting metal oxide morphologies could enhance fuel stability and design.

  16. SPECTROSCOPIC STUDIES OF STRUCTURE, DYNAMICS AND REACTIVITY IN IONIC LIQUIDS.

    SciTech Connect

    WISHART,J.F.

    2007-11-30

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate

  17. Reduction of Metal Oxide to Metal using Ionic Liquids

    SciTech Connect

    Dr. Ramana Reddy

    2012-04-12

    A novel pathway for the high efficiency production of metal from metal oxide means of electrolysis in ionic liquids at low temperature was investigated. The main emphasis was to eliminate the use of carbon and high temperature application in the reduction of metal oxides to metals. The emphasis of this research was to produce metals such as Zn, and Pb that are normally produced by the application of very high temperatures. The reduction of zinc oxide to zinc and lead oxide to lead were investigated. This study involved three steps in accomplishing the final goal of reduction of metal oxide to metal using ionic liquids: 1) Dissolution of metal oxide in an ionic liquid, 2) Determination of reduction potential using cyclic voltammetry (CV) and 3) Reduction of the dissolved metal oxide. Ionic liquids provide additional advantage by offering a wide potential range for the deposition. In each and every step of the process, more than one process variable has been examined. Experimental results for electrochemical extraction of Zn from ZnO and Pb from PbO using eutectic mixtures of Urea ((NH2)2CO) and Choline chloride (HOC2H4N(CH3)3+Cl-) or (ChCl) in a molar ratio 2:1, varying voltage and temperatures were carried out. Fourier Transform Infra-Red (FTIR) spectroscopy studies of ionic liquids with and without metal oxide additions were conducted. FTIR and induction coupled plasma spectroscopy (ICPS) was used in the characterization of the metal oxide dissolved ionic liquid. Electrochemical experiments were conducted using EG&G potentiostat/galvanostat with three electrode cell systems. Cyclic voltammetry was used in the determination of reduction potentials for the deposition of metals. Chronoamperometric experiments were carried out in the potential range of -0.6V to -1.9V for lead and -1.4V to -1.9V for zinc. The deposits were characterized using XRD and SEM-EDS for phase, morphological and elemental analysis. The results showed that pure metal was deposited on the cathode

  18. Morphology and Ionic Conductivity of Humidity-Responsive Polymerized Ionic Liquid Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Meek, Kelly; Ye, Yuesheng; Elabd, Yossef A.; Winey, Karen I.

    2014-03-01

    We present the ionic conductivity and morphology of humidity-responsive polymerized ionic liquid block copolymers (PIL BCPs), poly(methyl methacrylate- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-X), where X is a bromide (Br) or hydroxide (OH) anion, as a function of relative humidity (RH), temperature, and PIL composition (ϕPIL) . PIL BCPs were characterized by in situ small-angle X-ray scattering and electrochemical impedance spectroscopy. These PIL BCPs have microphase separated morphologies and long-range order increases as ϕPIL increases. Notably, ionic conductivity increases 3 to 4 orders of magnitude when RH increases from 30 to 90 percent. When ϕPIL is greater than 0.37, BCP ionic conductivity approaches or exceeds that of the homopolymer, suggesting that the dynamics in PIL microdomains mimic the homopolymer and long-range order aids ion transport. Moreover, over 60 percent of the BCP is nonconductive without a penalty in ion transport. When ϕPIL is less than 0.37, BCP conductivity is 1 to 2 orders of magnitude less than the homopolymer and non-conductive PMMA segments dominate ion transport, as expected. Ionic conductivities at 80 °C, 90 percent RH, are 7.6 mS/cm for the Br-containing BCP with ϕPIL = 0.53 and 25.0 mS/cm for the OH-containing BCP with ϕPIL = 0.50.

  19. 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

  20. Thermoreversible (Ionic-Liquid-Based) Aqueous Biphasic Systems

    PubMed Central

    Passos, Helena; Luís, Andreia; Coutinho, João A. P.; Freire, Mara G.

    2016-01-01

    The ability to induce reversible phase transitions between homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and suitable operating temperatures, is of crucial relevance in the design of separation processes. Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated superior performance as alternative extraction platforms, and their thermoreversible behaviour is here disclosed by the use of protic ILs. The applicability of the temperature-induced phase switching is further demonstrated with the complete extraction of two value-added proteins, achieved in a single-step. It is shown that these temperature-induced mono(bi)phasic systems are significantly more versatile than classical liquid-liquid systems which are constrained by their critical temperatures. IL-based ABS allow to work in a wide range of temperatures and compositions which can be tailored to fit the requirements of a given separation process. PMID:26843320

  1. Thermoreversible (Ionic-Liquid-Based) Aqueous Biphasic Systems

    NASA Astrophysics Data System (ADS)

    Passos, Helena; Luís, Andreia; Coutinho, João A. P.; Freire, Mara G.

    2016-02-01

    The ability to induce reversible phase transitions between homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and suitable operating temperatures, is of crucial relevance in the design of separation processes. Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated superior performance as alternative extraction platforms, and their thermoreversible behaviour is here disclosed by the use of protic ILs. The applicability of the temperature-induced phase switching is further demonstrated with the complete extraction of two value-added proteins, achieved in a single-step. It is shown that these temperature-induced mono(bi)phasic systems are significantly more versatile than classical liquid-liquid systems which are constrained by their critical temperatures. IL-based ABS allow to work in a wide range of temperatures and compositions which can be tailored to fit the requirements of a given separation process.

  2. Direct Observation of Ion Distributions near Electrodes in Ionic Polymer Actuators Containing Ionic Liquids

    PubMed Central

    Liu, Yang; Lu, Caiyan; Twigg, Stephen; Ghaffari, Mehdi; Lin, Junhong; Winograd, Nicholas; Zhang, Q. M.

    2013-01-01

    The recent boom of energy storage and conversion devices, exploiting ionic liquids (ILs) to enhance the performance, requires an in-depth understanding of this new class of electrolytes in device operation conditions. One central question critical to device performance is how the mobile ions accumulate near charged electrodes. Here, we present the excess ion depth profiles of ILs in ionomer membrane actuators (Aquivion/1-butyl-2,3-dimethylimidazolium chloride (BMMI-Cl), 27 μm thick), characterized directly by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) at liquid nitrogen temperature. Experimental results reveal that for the IL studied, cations and anions are accumulated at both electrodes. The large difference in the total volume occupied by the excess ions between the two electrodes cause the observed large bending actuation of the actuator. Hence we demonstrate that ToF-SIMS experiment provides great insights on the physics nature of ionic devices. PMID:23512124

  3. Triggering the Chemical Instability of an Ionic Liquid under High Pressure.

    PubMed

    Faria, Luiz F O; Nobrega, Marcelo M; Temperini, Marcia L A; Bini, Roberto; Ribeiro, Mauro C C

    2016-09-01

    Ionic liquids are an interesting class of materials due to their distinguished properties, allowing their use in an impressive range of applications, from catalysis to hypergolic fuels. However, the reactivity triggered by the application of high pressure can give rise to a new class of materials, which is not achieved under normal conditions. Here, we report on the high-pressure chemical instability of the ionic liquid 1-allyl-3-methylimidazolium dicyanamide, [allylC1im][N(CN)2], probed by both Raman and IR techniques and supported by quantum chemical calculations. Our results show a reaction occurring above 8 GPa, involving the terminal double bond of the allyl group, giving rise to an oligomeric product. The results presented herein contribute to our understanding of the stability of ionic liquids, which is of paramount interest for engineering applications. Moreover, gaining insight into this peculiar kind of reactivity could lead to the development of new or alternative synthetic routes to achieve, for example, poly(ionic liquids). PMID:27470147

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

    PubMed

    Murugappan, Krishnan; Silvester, Debbie S

    2016-01-28

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

  5. The capacitance of ionic liquid electric double layer near nanostructured electrodes

    NASA Astrophysics Data System (ADS)

    Park, Yun Sung; Ahn, Myung Mo; Kang, In Seok

    2015-11-01

    The electric double layer capacitors (EDLC) with nanostructured electrodes have attracted much attention of researchers due to their high power density and long life time. Recently, the ionic liquids are used as an electrolyte of EDLC owing to their electrochemical stability. When ionic liquids are used as an electrolyte, the interrelations between the electric double layer of ionic liquids and the nanostructured electrode must be studied. In this study, the EDLC systems with nanostructured electrodes and ionic liquids are simulated by solving the modified Poisson-Boltzmann equation proposed by Bazant, Storey, and Kornyshev with COMSOL Multiphysics. Several electrode geometries including exohedral, endohedral and arrayed shapes with different length scales are simulated. The potential and charge distributions in the normal direction to the electrode surface are analyzed. The capacitance per unit area is obtained and compared to that of flat electrode. The structure determines the space for counter-ion packing and co-ion gathering, thus has crucial effects on electric double layer capacitance. The critical increase of capacitance with nanoscale confined space is observed with low electrode potential. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (Grant Number: 2013R1A1A2011956).

  6. Ether-functionalized ionic liquid electrolytes for lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Nakamoto, Hirofumi; Suzuki, Yushi; Shiotsuki, Taishi; Mizuno, Fuminori; Higashi, Shougo; Takechi, Kensuke; Asaoka, Takahiko; Nishikoori, Hidetaka; Iba, Hideki

    2013-12-01

    Ionic liquids composed of N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (DEME), N-methyl-N-methoxyethylpiperidinium (PP1.1o2) cations functionalized with ethers, N-methyl-N-propylpiperidinium (PP13), and N-butyl-N-methylpyrrolidinium (P14) cations and the bis(trifluoromethanesulfonyl)amide (TFSA) anion are investigated for application as electrolytes in non-aqueous lithium-oxygen (Li-O2) batteries. The PP13-TFSA, P14-TFSA and DEME-TFSA ionic liquids have high oxygen radical stability. A comparison of the lithium supply capacity measured using pulse-gradient spin-echo NMR for 7Li nuclei and the oxygen supply capacity measured using electrochemical methods indicates that the oxygen supply is the rate-limiting step for the generation of lithium-oxygen compounds (LiOx) in these ionic liquids with supporting electrolytes. The DEME-TFSA system has the highest LiOx generation activity among the ionic liquid systems examined. We demonstrate the improved performance (output power, discharge-charge capacity and coulombic efficiency) of a Li-O2 battery using the DEME-TFSA system compared with that using the PP13-TFSA system. The improvements observed for the DEME-TFSA system are attributed to the high LiOx generation properties and lithium ion supply.

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

    PubMed

    Kiefer, Johannes; Pye, Cory C

    2010-06-24

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

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

    SciTech Connect

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

    2003-12-17

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

  9. Solvation structures of water in trihexyltetradecylphosphonium-orthoborate ionic liquids

    NASA Astrophysics Data System (ADS)

    Wang, Yong-Lei; Sarman, Sten; Kloo, Lars; Antzutkin, Oleg N.; Glavatskih, Sergei; Laaksonen, Aatto

    2016-08-01

    Atomistic molecular dynamics simulations have been performed to investigate effective interactions of isolated water molecules dispersed in trihexyltetradecylphosphonium-orthoborate ionic liquids (ILs). The intrinsic free energy changes in solvating one water molecule from gas phase into bulk IL matrices were estimated as a function of temperature, and thereafter, the calculations of potential of mean force between two dispersed water molecules within different IL matrices were performed using umbrella sampling simulations. The systematic analyses of local ionic microstructures, orientational preferences, probability and spatial distributions of dispersed water molecules around neighboring ionic species indicate their preferential coordinations to central polar segments in orthoborate anions. The effective interactions between two dispersed water molecules are partially or totally screened as their separation distance increases due to interference of ionic species in between. These computational results connect microscopic anionic structures with macroscopically and experimentally observed difficulty in completely removing water from synthesized IL samples and suggest that the introduction of hydrophobic groups to central polar segments and the formation of conjugated ionic structures in orthoborate anions can effectively reduce residual water content in the corresponding IL samples.

  10. Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

    SciTech Connect

    Fan, Fei; Wang, Yangyang; Hong, Tao; Heres, Maximilian F; Saito, Tomonori; Sokolov, Alexei P

    2015-01-01

    Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviation from the ideal line increases upon approaching the glass transition temperature (Tg). The conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. We relate this observation to a decrease in polymer packing efficiency with an increase in fragility.

  11. Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

    DOE PAGESBeta

    Fan, Fei; Wang, Yangyang; Hong, Tao; Heres, Maximilian F; Saito, Tomonori; Sokolov, Alexei P

    2015-01-01

    Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore » from the ideal line increases upon approaching the glass transition temperature (Tg). The conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. We relate this observation to a decrease in polymer packing efficiency with an increase in fragility.« less

  12. 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

  13. 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

  14. Liquid-liquid equilibria of binary mixtures of a lipidic ionic liquid with hydrocarbons.

    PubMed

    Green, Blane D; Badini, Alexander J; O'Brien, Richard A; Davis, James H; West, Kevin N

    2016-01-28

    Although structurally diverse, many ionic liquids (ILs) are polar in nature due to the strong coulombic forces inherent in ionic compounds. However, the overall polarity of the IL can be tuned by incorporating significant nonpolar content into one or more of the constituent ions. In this work, the binary liquid-liquid equilibria of one such IL, 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide, with several hydrocarbons (n-hexane, n-octane, n-decane, cyclohexane, methylcyclohexane, 1-octene) is measured over the temperature range 0-70 °C at ambient pressure using a combination of cloud point and gravimetric techniques. The phase behavior of the systems are similar in that they exhibit two phases: one that is 60-90 mole% hydrocarbon and a second phase that is nearly pure hydrocarbon. Each phase exhibits a weak dependence of composition on temperature (steep curve) above ∼10 °C, likely due to swelling and restructuring of the nonpolar nano-domains of the IL being limited by energetically unfavorable restructuring in the polar nano-domains. The solubility of the n-alkanes decreases with increasing size (molar volume), a trend that continues for the cyclic alkanes, for which upper critical solution temperatures are observed below 70 °C. 1-Octene is found to be more soluble than n-octane, attributable to a combination of its lower molar volume and slightly higher polarity. The COSMO-RS model is used to predict the T-x'-x'' diagrams and gives good qualitative agreement of the observed trends. This work presents the highest known solubility of n-alkanes in an IL to date and tuning the structure of the ionic liquid to maximize the size/shape trends observed may provide the basis for enhanced separations of nonpolar species. PMID:26700653

  15. Distinctive Nanoscale Organization of Dicationic versus Monocationic Ionic Liquids

    SciTech Connect

    Li, Song; Feng, Guang; Banuelos, Jose Leo; Rother, Gernot; Fulvio, Pasquale F; Dai, Sheng; Cummings, Peter T

    2013-01-01

    The distinctive structural organization of dicationic ionic liquids (DILs) with varying alkyl linkage chain lengths is systematically investigated using classical molecular dynamics (MD) simulations. In comparison with their counterparts, monocationic ionic liquids (MILs) with free alkyl chain, the DILs with short linkage chains exhibit almost identical structural features regardless of anion types, whereas the long-chain DILs display a relatively insignificant prepeak and low heterogeneity order parameter (HOP), which is accompanied by the less evident structural heterogeneity. Moreover, the predominant role of anion type in the structure of DILs was verified, similar to what is observed in MILs. Finally, the different nanoscale organizations in DILs and MILs are rationalized by the relatively unfavorable straight and folded chain models proposed for the nanoaggregates in DILs and the favorable micelle-like arrangement for those in MILs.

  16. Reactions of Lignin Model Compounds in Ionic Liquids

    SciTech Connect

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad

    2009-09-15

    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  17. Methanolysis of polycarbonate catalysed by ionic liquid [Bmim][Ac].

    PubMed

    Liu, Fusheng; Li, Lei; Yu, Shitao; Lv, Zhiguo; Ge, Xiaoping

    2011-05-15

    The methanolysis of polycarbonate (PC) was studied using ionic liquid [Bmim][Ac] as a catalyst. The effects of temperature, time, methanol dosage and [Bmim][Ac] dosage on the methanolysis reaction were examined. It was shown that the conversion of PC was nearly 100%, and the yield of bisphenol A (BPA) was over 95% under the following conditions: m([Bmim][Ac]):m(PC) = 0.75:1;m(methanol):m(PC) = 0.75:1; a reaction temperature of 90 °C and a total time of 2.5h. The ionic liquid could be reused up to 6 times with no apparent decrease in the conversion of PC and yield of BPA. The kinetics of the reaction was also investigated. The results indicated that the methanolysis of PC in [Bmim][Ac] was a first-order kinetic reaction with an activation energy of 167 kJ/mol. PMID:21402441

  18. Hydrolysis of polycarbonate catalyzed by ionic liquid [Bmim][Ac].

    PubMed

    Song, Xiuyan; Liu, Fusheng; Li, Lei; Yang, Xuequn; Yu, Shitao; Ge, Xiaoping

    2013-01-15

    Hydrolysis of polycarbonate (PC) was studied using ionic liquid 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]) as a catalyst. The influences of temperature, time, water dosage and [Bmim][Ac] dosage on the hydrolysis reaction were examined. Under the conditions of temperature 140°C, reaction time 3.0 h, m([Bmim][Ac]):m(PC)=1.5:1 and m(H(2)O):m(PC)=0.35:1, the conversion of PC was nearly 100% and the yield of bisphenol A (BPA) was over 96%. The ionic liquid could be reused up to 6 times without apparent decrease in the conversion of PC and yield of BPA. The kinetics of the reaction was also investigated. The results showed that the hydrolysis of PC in [Bmim][Ac] was a first-order kinetic reaction with an activation energy of 228 kJ/mol. PMID:23246956

  19. Ordered ionic liquid structure observed at terraced graphite interfaces.

    PubMed

    He, Xing; Wu, Chengyi; Rajagopal, Karjini; Punpongjareorn, Napat; Yang, Ding-Shyue

    2016-02-01

    Reflection high-energy electron diffraction is presented as a contactless, surface-specific method to probe the ion organization and layering at the ionic liquid-solid interfaces. Three regimes can be identified for the structure of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]) on highly oriented pyrolytic graphite, which is strongly dependent on the distances of ions from the surface. Direct observations showed that the ultrathin ionic liquid (IL) assembly can exhibit bulk-like phase-transition behaviours as a result of the structural matching between the IL and graphite layers and the confinement template effect due to the surface topography of graphite. The present study illustrates the opportunities for conducting further studies of the structures and ultrafast dynamics of IL-solid interfaces. PMID:26775813

  20. Synthesis and Characterization of Tetramethylethylenediamine-Based Hypergolic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Fei, Teng; Cai, Huiwu; Zhang, Yanqiang; Liu, Long; Zhang, Suojiang

    2016-04-01

    Four energetic salts (including two ionic liquids) based on 2-(dimethylamino)-N,N,N-trimethylethanaminium and N,N‧-dialkyl-N,N,N‧,N‧-tetramethylethane-1,2-diaminium was prepared and characterized by 1H- and 13C-NMR, infrared and Raman spectroscopies, and elemental analysis. Their physicochemical properties such as melting and decomposition temperatures, density, viscosity, heat of formation, detonation performance, and specific impulse were measured or calculated. With thermal stability up to 200°C, the resulting ionic liquids show densities from 1.02 to 1.19 g cm-3 and heats of formation from 85.1 to 154.4 kJ mol-1. Moreover, 2-(dimethylamino)-N,N,N-trimethylethanaminium dicyanamide is hypergolic with the oxidizer (100% HNO3) and exhibits potential as a green fuel for bipropellants.

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

    PubMed

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

    2007-08-30

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

  2. Maillard reaction products from chitosan-xylan ionic liquid solution.

    PubMed

    Luo, Yuqiong; Ling, Yunzhi; Wang, Xiaoying; Han, Yang; Zeng, Xianjie; Sun, Runcang

    2013-10-15

    A facile method is reported to prepare Maillard reaction products (MRPs) from chitosan and xylan in co-solvent ionic liquid. UV absorbance and fluorescence changes were regarded as indicators of the occurrence of Maillard reaction. FT-IR, NMR, XRD and TG were used to investigate the structure of chitosan-xylan conjugate. The results revealed that when chitosan reacted with xylan in ionic liquid, the hydrogen bonds in chitosan were destroyed, the facts resulted in the formation of chitosan-xylan MRPs. Moreover, when the mass ratio of chitosan to xylan was 1:1, the Maillard reaction proceeded easily. In addition, relatively high antioxidant property was also noted for the chitosan-xylan conjugate with mass ratio 1:1. So the obtained chitosan-xylan MRP is a promising antioxidant agent for food industry. PMID:23987419

  3. Betaine and Carnitine Derivatives as Herbicidal Ionic Liquids.

    PubMed

    Pernak, Juliusz; Niemczak, Michał; Chrzanowski, Łukasz; Ławniczak, Łukasz; Fochtman, Przemysław; Marcinkowska, Katarzyna; Praczyk, Tadeusz

    2016-08-16

    This study focused on the synthesis and subsequent characterization of herbicidal ionic liquids based on betaine and carnitine, two derivatives of amino acids, which were used as cations. Four commonly used herbicides (2,4-D, MCPA, MCPP and Dicamba) were used as anions in simple (single anion) and oligomeric (two anions) salts. The obtained salts were subjected to analyzes regarding physicochemical properties (density, viscosity, refractive index, thermal decomposition profiles and solubility) as well as evaluation of their herbicidal activity under greenhouse and field conditions, toxicity towards rats and biodegradability. The obtained results suggest that the synthesized herbicidal ionic liquids displayed low toxicity (classified as category 4 compounds) and showed similar or improved efficacy against weed compared to reference herbicides. The highest increase was observed during field trials for salts containing 2,4-D as the anion, which also exhibited the highest biodegradability (>75 %). PMID:27374836

  4. Ionic liquids for separation of olefin-paraffin mixtures

    DOEpatents

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2013-09-17

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  5. Ionic liquids for separation of olefin-paraffin mixtures

    DOEpatents

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2014-07-15

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  6. IONIC LIQUIDS: RADIATION CHEMISTRY, SOLVATION DYNAMICS AND REACTIVITY PATTERNS.

    SciTech Connect

    WISHART,J.F.

    2007-10-01

    energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate the influence of ILs on charge transport processes. Methods. Picosecond pulse radiolysis studies at BNL

  7. Ionic liquid-induced synthesis of selenium nanoparticles

    SciTech Connect

    Langi, Bhushan; Shah, Chetan; Singh, Krishankant; Chaskar, Atul; Kumar, Manmohan; Bajaj, Parma N.

    2010-06-15

    A simple wet chemical method has been used to synthesize selenium nanoparticles by the reaction of ionic liquid with sodium selenosulphate, a selenium precursor, in the presence of polyvinyl alcohol stabilizer, in aqueous medium. The method is capable of producing spherical selenium nanoparticles in the size range of 76-150 nm under ambient conditions. This is a first report on the production of nano-selenium assisted by an ionic liquid. The synthesized nanoparticles can be separated easily from the aqueous sol by a high-speed centrifuge machine, and can be re-dispersed in an aqueous medium. The synthesized selenium nanoparticles have been characterized by X-ray diffraction, energy dispersive X-ray analysis, differential scanning calorimetry and transmission electron microscopy techniques.

  8. Carbon films produced from ionic liquid carbon precursors

    DOEpatents

    Dai, Sheng; Luo, Huimin; Lee, Je Seung

    2013-11-05

    The invention is directed to a method for producing a film of porous carbon, the method comprising carbonizing a film of an ionic liquid, wherein the ionic liquid has the general formula (X.sup.+a).sub.x(Y.sup.-b).sub.y, wherein the variables a and b are, independently, non-zero integers, and the subscript variables x and y are, independently, non-zero integers, such that ax=by, and at least one of X.sup.+ and Y.sup.- possesses at least one carbon-nitrogen unsaturated bond. The invention is also directed to a composition comprising a porous carbon film possessing a nitrogen content of at least 10 atom %.

  9. Stable and water-tolerant ionic liquid ferrofluids.

    PubMed

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

    2011-03-01

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

  10. Antibacterial activities of fluorescent nano assembled triphenylamine phosphonium ionic liquids.

    PubMed

    Brunel, Frédéric; Lautard, Christelle; Garzino, Frédéric; Giorgio, Suzanne; Raimundo, Jean M; Bolla, Jean M; Camplo, Michel

    2016-08-01

    Staphylococcus aureus, a Gram positive coccal bacterium is a major cause of nosocomial infection. We report the synthesis of new triphenylamine phosphonium ionic liquids which are able to self-assemble into multiwall nanoassemblies and to reveal a strong bactericidal activity (MIC=0.5mg/L) for Gram positive bacteria (including resistant strains) comparable to that of standard antibiotics. Time kill, metabolism and fluorescence confocal microscopy studies show a quasi-instantaneously penetration of the nanoassemblies inside the bacteria resulting of a rapid blocking (30min) of their proliferation. As confirmed by rezasurin reduction monitoring, these compounds strongly affect the bacterial metabolism and a Gram positive versus Gram negative selectivity is clearly observed. These fluorescent phosphonium ionic liquid might constitute a useful tool for both translocation studies and to tackle infectious diseases related to the field of implantology. PMID:27287371

  11. Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xH(x-1)]-.

    PubMed

    Johansson, K M; Izgorodina, E I; Forsyth, M; MacFarlane, D R; Seddon, K R

    2008-05-28

    We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine-acetic acid mixtures. The simple 1 : 1 acid-base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)(x)H(x-1)](-) stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1 : 1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion. PMID:18473045

  12. MINOR ACTINIDE SEPARATIONS USING ION EXCHANGERS OR IONIC LIQUIDS

    SciTech Connect

    Hobbs, D.; Visser, A.; Bridges, N.

    2011-09-20

    This project seeks to determine if (1) inorganic-based ion exchange materials or (2) electrochemical methods in ionic liquids can be exploited to provide effective Am and Cm separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of inorganic-based ion-exchange materials for actinide and lanthanide ions. Furthermore, we seek to determine whether ionic liquids can serve as the electrolyte that would enable formation of higher oxidation states of Am and other actinides. Experiments indicated that pH, presence of complexants and Am oxidation state exhibit significant influence on the uptake of actinides and lanthanides by layered sodium titanate and hybrid zirconium and tin phosphonate ion exchangers. The affinity of the ion exchangers increased with increasing pH. Greater selectivity among Ln(III) ions with sodium titanate materials occurs at a pH close to the isoelectric potential of the ion exchanger. The addition of DTPA decreased uptake of Am and Ln, whereas the addition of TPEN generally increases uptake of Am and Ln ions by sodium titanate. Testing confirmed two different methods for producing Am(IV) by oxidation of Am(III) in ionic liquids (ILs). Experimental results suggest that the unique coordination environment of ionic liquids inhibits the direct electrochemical oxidation of Am(III). The non-coordinating environment increases the oxidation potential to a higher value, while making it difficult to remove the inner coordination of water. Both confirmed cases of Am(IV) were from the in-situ formation of strong chemical oxidizers.

  13. The Interactions between Imidazolium-Based Ionic Liquids and Stable Nitroxide Radical Species: A Theoretical Study.

    PubMed

    Zhang, Shaoze; Wang, Guimin; Lu, Yunxiang; Zhu, Weiliang; Peng, Changjun; Liu, Honglai

    2016-08-01

    In this work, the interactions between imidazolium-based ionic liquids and some stable radicals based on 2,2,6,6-tetramethylpiperidine-1-yloxyl (TEMPO) have been systematically investigated using density functional theory calculations at the level of M06-2x. Several different substitutions, such as hydrogen bonding formation substituent (OH) and ionic substituents (N(CH3)3(+) and OSO3(-)), are presented at the 4-position of the spin probe, which leads to additional hydrogen bonds or ionic interactions between these substitutions and ionic liquids. The interactions in the systems of the radicals containing ionic substitutions with ionic liquids are predicted much stronger than those in the systems of neutral radicals, resulting in a significant reduction of the mobility of ionic radicals in ionic liquids. To further understand the nature of these interactions, the natural bond order, atoms in molecules, noncovalent interaction index, electron density difference, energy decomposition analysis, and charge decomposition analysis schemes were employed. The additional ionic interactions between ionic radicals and counterions in ionic liquids are dominantly contributed from the electrostatic term, while the orbital interaction plays a major role in other interactions. The results reported herein are important to understand radical processes in ionic liquids and will be very useful in the design of task-specific ionic liquids to make the processes more efficient. PMID:27428048

  14. Pretreatment of Lignocellulosic Biomass with Low-cost Ionic Liquids.

    PubMed

    Gschwend, Florence J V; Brandt, Agnieszka; Chambon, Clementine L; Tu, Wei-Chien; Weigand, Lisa; Hallett, Jason P

    2016-01-01

    A number of ionic liquids (ILs) with economically attractive production costs have recently received growing interest as media for the delignification of a variety of lignocellulosic feedstocks. Here we demonstrate the use of these low-cost protic ILs in the deconstruction of lignocellulosic biomass (Ionosolv pretreatment), yielding cellulose and a purified lignin. In the most generic process, the protic ionic liquid is synthesized by accurate combination of aqueous acid and amine base. The water content is adjusted subsequently. For the delignification, the biomass is placed into a vessel with IL solution at elevated temperatures to dissolve the lignin and hemicellulose, leaving a cellulose-rich pulp ready for saccharification (hydrolysis to fermentable sugars). The lignin is later precipitated from the IL by the addition of water and recovered as a solid. The removal of the added water regenerates the ionic liquid, which can be reused multiple times. This protocol is useful to investigate the significant potential of protic ILs for use in commercial biomass pretreatment/lignin fractionation for producing biofuels or renewable chemicals and materials. PMID:27583830

  15. Rheology of Imidazolium-Based Ionic Liquids with Aromatic Functionality.

    PubMed

    Tao, Ran; Simon, Sindee L

    2015-09-01

    A series of imidazolium-based ionic liquids with cyclic and aromatic groups and a bis[(trifluoromethane)sulfonyl]amide anion were characterized using dynamic and steady shear rheology in a wide temperature range. The cations investigated include 1-(cyclohexylmethyl)-3-methylimidazolium ([CyhmC1im](+)), 1-benzyl-3-methylimidazolium ([BnzC1im](+)), 1,3-dibenzylimidazolium ([(Bnz)2im](+)), and 1-(2-naphthylmethyl)-3-methylimidazolium ([NapmC1im](+)). Rheological properties are reported from terminal flow to the glassy state. All ionic liquids show very similar flow behavior with a glassy modulus approaching 1 GPa. The temperature dependences of the shift factors used for time-temperature superposition and the viscosity both follow the same VFT or WLF relationship, and the dynamic fragility at Tg ranges from 117 to 130 for the aromatic ionic liquids investigated, considerably more fragile, in the Angell sense, than the aliphatic analogs. Additionally, an anomalous aging effect in the dynamic viscosity response (i.e., a maximum observed at intermediate frequencies) was found using a strain-controlled rheometer but not using a stress-controlled rheometer. PMID:26230926

  16. Understanding the impact of ionic liquid pretreatment on eucalyptus

    SciTech Connect

    Centikol, Ozgul; Dibble, Dean; Cheng, Gang; Kent, Michael S; Knierim, Manfred; Melnichenko, Yuri B

    2010-01-01

    The development of cost-competitive biofuels necessitates the realization of advanced biomass pretreatment technologies. Ionic liquids provide a basis for one of the most promising pretreatment technologies and are known to allow effective processing of cellulose and some biomass species. Here, we demonstrate that the ionic liquid 1-ethyl-3-methyl imidazolium acetate, [C2mim][OAc], induces structural changes at the molecular level in the cell wall of Eucalyptus globulus. Deacetylation of xylan, acetylation of the lignin units, selective removal of guaiacyl units (increasing the syringyl:guaiacyl ratio) and decreased {beta}-ether content were the most prominent changes observed. Scanning electron microscopy images of the plant cell wall sections reveal extensive swelling during [C2mim][OAc] pretreatment. X-ray diffraction measurements indicate a change in cellulose crystal structure from cellulose I to cellulose II after [C2mim][OAc] pretreatment. Enzymatic saccharification of the pretreated material produced increased sugar yields and improved hydrolysis kinetics after [C2mim][OAc] pretreatment. These results provide new insight into the mechanism of ionic liquid pretreatment and reaffirm that this approach may be promising for the production of cellulosic biofuels from woody biomass.

  17. MD Study of Stokes Shifts in Ionic Liquids: Temperature Dependence.

    PubMed

    Wu, Eric C; Kim, Hyung J

    2016-05-26

    Effects of temperature on Stokes shifts, solvation structure, and dynamics in ionic liquids EMI(+)Tf2N(-), EMI(+)PF6(-), and BMI(+)PF6(-) (EMI(+) = 1-ethyl-3-methylimidazolium, BMI(+) = 1-butyl-3-methylimidazolium, Tf2N(-) = bis(trifluoromethylsulfonyl)imide, and PF6(-) = hexafluorophosphate) are investigated via molecular dynamics (MD) computer simulations in the temperature range 350 K ≤ T ≤ 500 K. Two different types of solutes are considered: a simple model diatomic solute and realistic coumarin 153, both of which are characterized by more polar S1 and less polar S0 states. In all three ionic liquids studied, the Stokes shift tends to decrease with increasing temperature. For coumarin 153, as T increases, the Franck-Condon energy for steady-state absorption decreases, whereas that for steady-state emission increases. Our findings indicate that the effective polarity of ionic liquids decreases as T increases. Their solvation dynamics are characterized by an ultrafast initial decay in the subpicosecond time scale, followed by slow dissipative relaxation, regardless of temperature. For both solutes, the solvent frequency that quantifies initial ultrafast dynamics shows little temperature dependence. By contrast, the long-time dissipative dynamics become significantly faster with rising T. Variations of solvation structure with temperature and their connection to Stokes shift and solvation dynamics are briefly examined. PMID:27133895

  18. Carbons, ionic liquids and quinones for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Diaz, Raul; Doherty, Andrew

    2016-04-01

    Carbons are the main electrode materials used in electrochemical capacitors, which are electrochemical energy storage devices with high power densities and long cycling lifetimes. However, increasing their energy density will improve their potential for commercial implementation. In this regard, the use of high surface area carbons and high voltage electrolytes are well known strategies to increase the attainable energy density, and lately ionic liquids have been explored as promising alternatives to current state of the art acetonitrile-based electrolytes. Also, in terms of safety and sustainability ionic liquids are attractive electrolyte materials for electrochemical capacitors. In addition, it has been shown that the matching of the carbon pore size with the electrolyte ion size further increases the attainable electric double layer (EDL) capacitance and energy density. The use of pseudocapacitive reactions can significantly increase the attainable energy density, and quinonic-based materials offer a potentially sustainable and cost effective research avenue for both the electrode and the electrolyte. This perspective will provide an overview of the current state of the art research on electrochemical capacitors based on combinations of carbons, ionic liquids and quinonic compounds, highlighting performances and challenges and discussing possible future research avenues. In this regard, current interest is mainly focused on strategies which may ultimately lead to commercially competitive sustainable high performance electrochemical capacitors for different applications including those requiring mechanical flexibility and biocompatibility.

  19. The solvation structures of cellulose microfibrils in ionic liquids

    SciTech Connect

    Mostofian, Barmak; Smith, Jeremy C; Cheng, Xiaolin

    2011-01-01

    The use of ionic liquids for non-derivatized cellulose dissolution promises an alternative method for the thermochemical pretreatment of biomass that may be more efficient and environmentally acceptable than more conventional techniques in aqueous solution. Here, we performed equilibrium MD simulations of a cellulose microfibril in the ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and compared the solute structure and the solute-solvent interactions at the interface with those from corresponding simulations in water. The results indicate a higher occurrence of solvent-exposed orientations of cellulose surface hydroxymethyl groups in BmimCl than in water. Moreover, spatial and radial distribution functions indicate that hydrophilic surfaces are a preferred site of interaction between cellulose and the ionic liquid. In particular, hydroxymethyl groups on the hydrophilic fiber surface adopt a different conformation from their counterparts oriented towards the fiber s core. Furthermore, the glucose units with these solvent-oriented hydroxymethyls are surrounded by the heterocyclic organic cation in a preferred parallel orientation, suggesting a direct and distinct interaction scheme between cellulose and BmimCl.

  20. Application of Ionic Liquids in Pot-in-Pot Reactions.

    PubMed

    Çınar, Simge; Schulz, Michael D; Oyola-Reynoso, Stephanie; Bwambok, David K; Gathiaka, Symon M; Thuo, Martin

    2016-01-01

    Pot-in-pot reactions are designed such that two reaction media (solvents, catalysts and reagents) are isolated from each other by a polymeric membrane similar to matryoshka dolls (Russian nesting dolls). The first reaction is allowed to progress to completion before triggering the second reaction in which all necessary solvents, reactants, or catalysts are placed except for the starting reagent for the target reaction. With the appropriate trigger, in most cases unidirectional flux, the product of the first reaction is introduced to the second medium allowing a second transformation in the same glass reaction pot-albeit separated by a polymeric membrane. The basis of these reaction systems is the controlled selective flux of one reagent over the other components of the first reaction while maintaining steady-state catalyst concentration in the first "pot". The use of ionic liquids as tools to control chemical potential across the polymeric membranes making the first pot is discussed based on standard diffusion models-Fickian and Payne's models. Besides chemical potential, use of ionic liquids as delivery agent for a small amount of a solvent that slightly swells the polymeric membrane, hence increasing flux, is highlighted. This review highlights the critical role ionic liquids play in site-isolation of multiple catalyzed reactions in a standard pot-in-pot reaction. PMID:26927045

  1. Predictive model for ionic liquid extraction solvents for rare earth elements

    NASA Astrophysics Data System (ADS)

    Grabda, Mariusz; Oleszek, Sylwia; Panigrahi, Mrutyunjay; Kozak, Dmytro; Eckert, Franck; Shibata, Etsuro; Nakamura, Takashi

    2015-12-01

    The purpose of our study was to select the most effective ionic liquid extraction solvents for dysprosium (III) fluoride using a theoretical approach. Conductor-like Screening Model for Real Solvents (COSMO-RS), based on quantum chemistry and the statistical thermodynamics of predefined DyF3-ionic liquid systems, was applied to reach the target. Chemical potentials of the salt were predicted in 4,400 different ionic liquids. On the base of these predictions set of ionic liquids' ions, manifesting significant decrease of the chemical potentials, were selected. Considering the calculated physicochemical properties (hydrophobicity, viscosity) of the ionic liquids containing these specific ions, the most effective extraction solvents for liquid-liquid extraction of DyF3 were proposed. The obtained results indicate that the COSMO-RS approach can be applied to quickly screen the affinity of any rare earth element for a large number of ionic liquid systems, before extensive experimental tests.

  2. Preparation of AgX (X = Cl, I) nanoparticles using ionic liquids

    NASA Astrophysics Data System (ADS)

    Rodil, Eva; Aldous, Leigh; Hardacre, Christopher; Lagunas, M. Cristina

    2008-03-01

    Nanoparticles of silver halides have been prepared by mixing silver halide powder with a single liquid phase consisting of an ionic liquid, isooctane, n-decanol and water. Much higher nanoparticle concentrations may be formed with ionic liquids using this new simple method than are found with conventionally applied surfactants. This method also emphasizes the applicability of ionic liquids as versatile components in microemulsions and as solvents for the synthesis of nanomaterials. The effect on the nanoparticles of changing the composition of the liquid mixtures and the nature of the ionic liquid is analysed. High nanoparticle concentrations were only found with chloride based ionic liquids, indicating the importance of the ionic liquid anion in the mechanism of the reaction.

  3. 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

  4. Electromechanical performance and membrane stability of novel ionic polymer transducers constructed in the presence of ionic liquids

    NASA Astrophysics Data System (ADS)

    Duncan, Andrew J.; Leo, Donald J.; Long, Timothy E.; Akle, Barbar J.; Park, Jong K.; Moore, Robert B.

    2009-03-01

    Ionic polymer transducers (IPT) are a class of devices that leverage electroactive polymers (EAP), specifically electrolyte-swollen ionomeric membranes, to perform energy conversions. Energy transformation from input to output is referred to as transduction and occurs between the electrical and mechanical domains. The present study expands on IPT investigations with a novel series of sulfonated polysulfones (sBPS), with specific interest in the effect of polymer topology on actuator performance. A hydrophilic ionic liquid was combined with a series of sBPS through a casting method to create hydrated membranes that contained target uptakes (f) of the diluent. The ionic liquid's hydrophilic, yet organic nature raised the issue of its degree of compatibility and miscibility with the microphase separated domains of the host ionomeric membrane. Initial studies of the ionomer - ionic liquid morphology were performed with synchrotron small angle X-ray scattering (SAXS). The effective plasticization of the membranes was identified with dynamic mechanical analysis (DMA) in terms of varied storage modulus and thermal transitions with ionic liquid uptake. Electrical impedance spectroscopy (EIS) was employed to quantify the changes in ionic conductivity for each sBPS ionomer across a range of uptake. Combined results from these techniques implied that the presence of large amounts of ionic liquid swelled the hydrophilic domains of the ionomer and greatly increased the ionic conductivity. Decreases in storage modulus and the glass transition temperature were proportional to one another but of a lesser magnitude than changes in conductivity. The present range of ionic liquid uptake for sBPS was sufficient to identify the critical uptake (fc) for three of the four ionomers in the series. Future work to construct IPTs with these components will use the critical uptake as a minimum allowable content of ionic liquid to optimize the balance of electrical and mechanical properties for

  5. Tandem dissolution of UO3 in amide-based acidic ionic liquid and in situ electrodeposition of UO2 with regeneration of the ionic liquid: a closed cycle.

    PubMed

    Wanigasekara, Eranda; Freiderich, John W; Sun, Xiao-Guang; Meisner, Roberta A; Luo, Huimin; Delmau, Lætitia H; Dai, Sheng; Moyer, Bruce A

    2016-06-21

    A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO3 to UO2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid [DMAH][NTf2] in [EMIM][NTf2] serving as the diluent. A sequential dissolution, electroreduction, and regeneration cycle is presented. PMID:27255672

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

    PubMed

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

    2009-10-23

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

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

    PubMed

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

    2009-12-01

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

  8. Electronically and ionically conductive gels of ionic liquids and charge-transfer tetrathiafulvalene-tetracyanoquinodimethane.

    PubMed

    Mei, Xiaoguang; Ouyang, Jianyong

    2011-09-01

    Electronically and ionically conductive gels were fabricated by mixing and mechanically grinding neutral tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ) in ionic liquids (ILs) like 3-ethyl-1-methylimidazolium dicyanoamide (EMIDCA), 1-ethyl-3-methylimidazolium thiocyanate (EMISCN), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITf(2)N), trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide (P(14,6,6,6)Tf(2)N), and methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide (MOATf(2)N). Charge-transfer TTF-TCNQ crystallites were generated during the mechanical grinding as indicated by the UV-visibile-near-infrared (UV-vis-NIR) absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction. The charge-transfer TTF-TCNQ crystallites have a needle-like shape. They form solid networks to gelate the ILs. The gel behavior is confirmed by the dynamic mechanical measurements. It depends on both the anions and cations of the ILs. In addition, when 1-methyl-3-butylimidazolium tetrafluoroborate (BMIBF(4)) and 1-methyl-3-propylimidazolium iodide (PMII) were used, the TTF-TCNQ/IL mixtures did not behave as gels. The TTF-TCNQ/IL gels are both electronically and ionically conductive, because the solid phase formed by the charge-transfer TTF-TCNQ crystallites is electronically conductive, while the ILs are ionically conductive. The gel formation is related to needle-like charge-transfer TTF-TCNQ cyrstallites and the π-π and Coulombic interactions between TTF-TCNQ and ILs. PMID:21800893

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

    PubMed

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

    2013-12-16

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

  10. Effect of pyrrolidinium based ionic liquid on the channel form of gramicidin in lipid vesicles.

    PubMed

    Singh, Upendra Kumar; Dohare, Neeraj; Mishra, Prabhash; Singh, Prashant; Bohidar, Himadri B; Patel, Rajan

    2015-08-01

    The present work is focused on the interaction between membrane bound gramicidin and 1-butyl-1-methyl-2-oxopyrrolidinium bromide (BMOP) ionic liquid. Ionic liquids (ILs) are solvents that are often liquid at room temperature and composed of organic cation and appropriate anion. The gramicidin peptide forms prototypical ion channels for cations, which have been extensively used to study the organization, dynamics, and function of membrane spanning channels. The interaction was studied by circular dichroism, steady state, time-resolved fluorescence spectroscopy in combination with dynamic surface tension and field emission scanning electron microscopic methods (FESEM). The results obtained from circular dichroism shows that the BMOP interacts with the channel form of gramicidin in lipid vesicle without any considerable effect on its conformation. The Red-edge excitation shift (REES) also supported the above findings. In addition, the fluorescence studies suggested that BMOP makes ground state complex with ion channel, which was further supported by time resolved measurements. Furthermore, dynamic surface tension analysis shows the faster adsorption of BMOP with membrane bound gramicidin at the air-water interface. Additionally, FESEM results indicated that BMOP forms a film around the membrane bound gramicidin at higher concentration. These results are potentially useful to analyze the effect of ionic liquids on the behaviour of membrane proteins. PMID:26025771

  11. Influence of Nanosegregation on the Surface Tension of Fluorinated Ionic Liquids.

    PubMed

    Luís, Andreia; Shimizu, Karina; Araújo, João M M; Carvalho, Pedro J; Lopes-da-Silva, José A; Canongia Lopes, José N; Rebelo, Luís Paulo N; Coutinho, João A P; Freire, Mara G; Pereiro, Ana B

    2016-06-21

    We have investigated, both theoretically and experimentally, the balance between the presence of alkyl and perfluoroalkyl side chains on the surface organization and surface tension of fluorinated ionic liquids (FILs). A series of ionic liquids (ILs) composed of 1-alkyl-3-methylimidazolium cations ([CnC1im] with n = 2, 4, 6, 8, 10, or 12) combined with the perfluorobutanesulfonate anion was used. The surface tensions of the investigated liquid salts are considerably lower than those reported for non-fluorinated ionic liquids. The most surprising and striking feature is the identification, for the first time, of a minimum at n = 8 in the surface tension versus the length of the IL cation alkyl side chain. Supported by molecular dynamics (MD) simulations, it was found that this trend is a result of the competition between the two nonpolar domains (perfluorinated and aliphatic) pointing toward the gas-liquid interface, a phenomenon which occurs in ILs with perfluorinated anions. Furthermore, these ILs present the lowest surface entropy reported to date. PMID:27218210

  12. Homogeneous liquid-liquid extraction of rare earths with the betaine-betainium bis(trifluoromethylsulfonyl)imide ionic liquid system.

    PubMed

    Vander Hoogerstraete, Tom; Onghena, Bieke; Binnemans, Koen

    2013-01-01

    Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature. PMID:24169434

  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. 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.

  15. Predictive model for ionic liquid extraction solvents for rare earth elements

    SciTech Connect

    Grabda, Mariusz; Oleszek, Sylwia; Panigrahi, Mrutyunjay; Kozak, Dmytro; Shibata, Etsuro; Nakamura, Takashi; Eckert, Franck

    2015-12-31

    The purpose of our study was to select the most effective ionic liquid extraction solvents for dysprosium (III) fluoride using a theoretical approach. Conductor-like Screening Model for Real Solvents (COSMO-RS), based on quantum chemistry and the statistical thermodynamics of predefined DyF{sub 3}-ionic liquid systems, was applied to reach the target. Chemical potentials of the salt were predicted in 4,400 different ionic liquids. On the base of these predictions set of ionic liquids’ ions, manifesting significant decrease of the chemical potentials, were selected. Considering the calculated physicochemical properties (hydrophobicity, viscosity) of the ionic liquids containing these specific ions, the most effective extraction solvents for liquid-liquid extraction of DyF{sub 3} were proposed. The obtained results indicate that the COSMO-RS approach can be applied to quickly screen the affinity of any rare earth element for a large number of ionic liquid systems, before extensive experimental tests.

  16. Novel polymer electrolytes based on gelatin and ionic liquids

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  17. Novel Brønsted acidic ionic liquids and their use as dual solvent-catalysts.

    PubMed

    Cole, Amanda C; Jensen, Jessica L; Ntai, Ioanna; Tran, Kim Loan T; Weaver, Kristin J; Forbes, David C; Davis, James H

    2002-05-29

    The reaction of triphenylphosphine or N-butylimidazole with cyclic sultones gives zwitterions that are subsequently converted into ionic liquids by reaction with trifluoromethane sulfonic acid or p-toluenesulfonic acid. The resulting ionic liquids have cations to which are tethered alkane sulfonic acid groups. These Brønsted acidic ionic liquids are useful solvent/catalysts for several organic reactions, including Fischer esterification, alcohol dehydrodimerization and the pinacol rearrangement. The new ionic liquids combine the low volatility and ease of separation from product normally associated with solid acid catalysts, with the higher activity and yields normally found using conventional liquid acids. PMID:12022828

  18. Application of Ionic Liquids in High Performance Reversed-Phase Chromatography

    PubMed Central

    Wang, Ye; Tian, Minglei; Bi, Wentao; Row, Kyung Ho

    2009-01-01

    Ionic liquids, considered “green” chemicals, are widely used in many areas of analytical chemistry due to their unique properties. Recently, ionic liquids have been used as a kind of novel additive in separation and combined with silica to synthesize new stationary phase as separation media. This review will focus on the properties and mechanisms of ionic liquids and their potential applications as mobile phase modifier and surface-bonded stationary phase in reversed-phase high performance liquid chromatography (RP-HPLC). Ionic liquids demonstrate advantages and potential in chromatographic field. PMID:19582220

  19. Partition coefficients of organic compounds in new imidazolium based ionic liquids using inverse gas chromatography.

    PubMed

    Revelli, Anne-Laure; Mutelet, Fabrice; Jaubert, Jean-Noël

    2009-06-01

    Partition coefficients of organic compounds in four ionic liquids: 1-ethanol-3-methylimidazolium tetrafluoroborate, 1-ethanol-3-methylimidazolium hexafluorophosphate, 1,3-dimethylimidazolium dimethylphosphate and 1-ethyl-3-methylimidazolium diethylphosphate were measured using inverse gas chromatography from 303.3 to 332.55K. The influence of gas-liquid and gas-solid interfacial adsorption of different solutes on ionic liquids was also studied. Most of the polar solutes were retained largely by partition while light hydrocarbons were retained predominantly by interfacial adsorption on the ionic liquids studied in this work. The solvation characteristics of the ionic liquids were evaluated using the Abraham solvation parameter model. PMID:19414174

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

    PubMed

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

    2014-01-28

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

  1. Modulating the Solubilities of Ionic Liquid Components in Aqueous-Ionic Liquid Biphasic Systems: A Q-NMR Investigation.

    PubMed

    Atanassova, Maria; Mazan, Valérie; Billard, Isabelle

    2015-06-01

    Aqueous-ionic liquid (A-IL) biphasic systems have been examined in terms of deuterated water, acid, and IL cation and anion mutual solubilities in the upper (water-rich, in mole fraction) and lower phase of aqueous/IL biphasic systems at ambient temperature. The biphasic mixtures were composed of deuterated acids of various concentrations (mainly DCl, DNO(3), and DClO(4) from 10(-2) to 10(-4)  M) and five ionic liquids of the imidazolium family with a hydrophobic anion (CF(3)SO(2))(2) N(-), that is, [C1 Cn im][Tf(2)N], (n=2, 4, 6, 8 and 10). The analytical techniques applied were (1) H NMR, (19) F NMR, Karl-Fischer titration, pH potentiometry for IL cations and anions, and water and acid determination. The effects of the ionic strength (μ=0.1 M NaCl and NaNO(3) as well as μ=0.1 M, 0.2 M and 0.4 M NaClO(4), according to the investigated acid), the nature of the IL cation, and the nature of the mineral acid on the solubilities of the (D(2)O, D(+), Tf(2)N(-), C1 Cn im(+)) entities in the lower or upper phases were determined. The addition of sodium perchlorate was found to enhance the Tf(2)N(-) solubility while inhibiting the solubility of the ionic liquid cation. Differences in IL cation and anion solubilities of up to 42 mM were evidenced. The consequences for the characterization of the aqueous biphasic system, the solvent extraction process of the metal ions, and the ecological impact of the ILs are discussed. PMID:25787248

  2. GEC Student Award for Excellence Finalist: Creation of Stable Plasma-Liquid Interfaced Reactive Field using Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Baba, Kazuhiko; Kaneko, Toshiro; Hatakeyama, Rikizo

    2008-10-01

    The gas-liquid interfacial region which is the boundary between plasmas and liquids, activating physical and chemical reactions, has attracted much attention as novel reactive field in nano-bio material creation. Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we succeeded in creating the reactive gas (plasmas)-liquid (ionic liquids) interfacial field under a low gas pressure condition, where the plasma ion behavior can be controlled. The effects of plasma ion irradiation on the liquid medium are for the first time quantitatively revealed. In connection with the plasma ion irradiation, the potential structure and optical emission properties of the gas-liquid interfacial plasma are investigated by changing a polarity of the ionic liquid electrode in order to evaluate the ionic liquid-plasma interactions. These results would contribute to systematizing the field of gas-liquid interfacial plasma physics for its applications.

  3. Ion shape effect on dynamics of ionic liquids

    NASA Astrophysics Data System (ADS)

    Liu, Hongjun; Maginn, Edward

    2012-02-01

    Ionic liquids (ILs) are a group of salts composing of an organic cation and organic or inorganic anion with melting points below 100 ^oC and have many suitable properties, such as negligible vapor pressure, low flammability, high ionic conductivity and high thermal stability for various applications. Moreover, a great number of ILs with a variety of physical and chemical properties can be synthesized from a combination of different cations (most differently substituted imidazolium, pyridinium, and quaternary ammonium or phosphonium ions) and anions. One can judiciously select from a multitude of ILs to suit a specific application, where the concept of designer solvent comes from. To expedite the development process of target ILs, it is crucial to understand the relationship between ion shape and dynamics of ILs. We studied a wide range of ILs with different ion shape pairings and found the planar-planar paired ILs have a better dynamics as a whole.

  4. Graphene/Ionic liquid composite films and ion exchange.

    PubMed

    Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

    2014-01-01

    Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

  5. Graphene/Ionic Liquid Composite Films and Ion Exchange

    NASA Astrophysics Data System (ADS)

    Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

    2014-06-01

    Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force.

  6. A Triphasic Sorting System: Coordination Cages in Ionic Liquids.

    PubMed

    Grommet, Angela B; Bolliger, Jeanne L; Browne, Colm; Nitschke, Jonathan R

    2015-12-01

    Host-guest chemistry is usually carried out in either water or organic solvents. To investigate the utility of alternative solvents, three different coordination cages were dissolved in neat ionic liquids. By using (19) F NMR spectroscopy to monitor the presence of free and bound guest molecules, all three cages were demonstrated to be stable and capable of encapsulating guests in ionic solution. Different cages were found to preferentially dissolve in different phases, allowing for the design of a triphasic sorting system. Within this system, three coordination cages, namely Fe4 L6 2, Fe8 L12 3, and Fe4 L4 4, each segregated into a distinct layer. Upon the addition of a mixture of three different guests, each cage (in each separate layer) selectively bound its preferred guest. PMID:26494225

  7. Graphene/Ionic Liquid Composite Films and Ion Exchange

    PubMed Central

    Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

    2014-01-01

    Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

  8. Novel thiosalicylate-based ionic liquids for heavy metal extractions.

    PubMed

    Leyma, Raphlin; Platzer, Sonja; Jirsa, Franz; Kandioller, Wolfgang; Krachler, Regina; Keppler, Bernhard K

    2016-08-15

    This study aims to develop novel ammonium and phosphonium ionic liquids (ILs) with thiosalicylate (TS) derivatives as anions and evaluate their extracting efficiencies towards heavy metals in aqueous solutions. Six ILs were synthesized, characterized, and investigated for their extracting efficacies for cadmium, copper, and zinc. Liquid-liquid extractions of Cu, Zn, or Cd with ILs after 1-24h using model solutions (pH 7; 0.1M CaCl2) were assessed using flame atomic absorption spectroscopy (F-AAS). Phosphonium-based ILs trihexyltetradecylphosphonium 2-(propylthio)benzoate [P66614][PTB] and 2-(benzylthio)benzoate [P66614][BTB] showed best extraction efficiency for copper and cadmium, respectively and zinc was extracted to a high degree by [P66614][BTB] exclusively. PMID:27131456

  9. Mass and Charge Transport in the Polymer-Ionic-Liquid System PEO-EMImI: From Ionic-Liquid-in-Polymer to Polymer-in-Ionic-Liquid Electrolytes.

    PubMed

    Kösters, Johannes; Schönhoff, Monika; Stolwijk, Nicolaas A

    2015-04-30

    Conventional polymer electrolytes based on inorganic salts are commonly characterized and utilized over a small salt-poor composition range because of phase transitions accompanied by loss of ion conductivity at high salt concentrations. By contrast, well-chosen polymer-ionic-liquid (IL) systems offer the possibility to vary the IL content from the IL-in-polymer to the polymer-in-IL domain. We have investigated the temperature-dependent ionic conductivity in PEOyEMImI systems consisting of poly(ethylene oxide) complexed with 1-ethyl-3-methylimidazolium iodide for y = EO/IL ratios ranging from 0.6 to 60 and compared diffusivity data with that arising from (1)H pulsed-field-gradient nuclear magnetic resonance for EMIm and (125)I radiotracer diffusion for iodine. Surprisingly, the diffusivity of cations and anions vary at most by 50% at fixed temperatures over the entire composition range. The much larger changes in the charge diffusivity Dσ relate to ion pairing exhibiting a minimum near the intermediate composition y = 10. Altogether, the results are relevant to application in dye-sensitized solar cells and show that a high ion density is crucial to enhance the iodine transport capacity. PMID:25848686

  10. 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

  11. A novel ionic liquid-tolerant Fusarium oxysporum BN secreting ionic liquid-stable cellulase: consolidated bioprocessing of pretreated lignocellulose containing residual ionic liquid.

    PubMed

    Xu, Jiaxing; Wang, Xinfeng; Hu, Lei; Xia, Jun; Wu, Zhen; Xu, Ning; Dai, Benlin; Wu, Bin

    2015-04-01

    In this study, microbial communities from chemicals polluted microhabitats were cultured with the addition of imidazolium-based ionic liquid (IL) to enrich for IL-tolerant microbes. A strain of Fusarium oxysporum BN producing cellulase from these enrichments was capable of growing in 10% (w/v) 1-ethyl-3-methylimidazolium phosphinate, much higher than the normal IL concentrations in the lignocellulose regenerated from ILs. Cellulase secreted by the strain showed high resistance to ILs based on phosphate and sulfate radicals, evidencing of a high conformational stability in relevant media. Gratifyingly, F. oxysporum BN can directly convert IL-pretreated rice straw to bioethanol via consolidated bioprocessing (I-CBP). At optimum fermentation condition, a maximum ethanol yield of 0.125 g ethanol g(-1) of rice straw was finally obtained, corresponding to 64.2% of the theoretical yield. PMID:25625459

  12. Can ionic liquids be used as templating agents for controlled design of uranium-containing nanomaterials?

    SciTech Connect

    Visser, Ann E. Bridges, Nicholas J.; Tosten, Michael H.

    2013-09-01

    Graphical abstract: - Highlights: • Uranium oxides nanoparticles prepared using ionic liquids. • IL cation alkyl length impacts oxide morphology. • Low temperature UO{sub 2} synthesis. - Abstract: Nanostructured uranium oxides have been prepared in ionic liquids as templating agents. Using the ionic liquids as reaction media for inorganic nanomaterials takes advantage of the pre-organized structure of the ionic liquids which in turn controls the morphology of the inorganic nanomaterials. Variation of ionic liquid cation structure was investigated to determine the impact on the uranium oxide morphologies. For two ionic liquid cations, increasing the alkyl chain length increases the aspect ratio of the resulting nanostructured oxides. Understanding the resulting metal oxide morphologies could enhance fuel stability and design.

  13. 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.

  14. Ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction for the separation and determination of estrogens in water samples by high-performance liquid chromatography with fluorescence detection.

    PubMed

    Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke

    2014-11-01

    An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened. PMID:25146581

  15. Surface science and model catalysis with ionic liquid-modified materials.

    PubMed

    Steinrück, H-P; Libuda, J; Wasserscheid, P; Cremer, T; Kolbeck, C; Laurin, M; Maier, F; Sobota, M; Schulz, P S; Stark, M

    2011-06-17

    Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy. PMID:21520462

  16. Thermodynamic studies of ionic hydration and interactions for amino acid ionic liquids in aqueous solutions at 298.15 K.

    PubMed

    Dagade, Dilip H; Madkar, Kavita R; Shinde, Sandeep P; Barge, Seema S

    2013-01-31

    Amino acid ionic liquids are a special class of ionic liquids due to their unique acid-base behavior, biological significance, and applications in different fields such as templates in synthetic chemistry, stabilizers for biological macromolecules, etc. The physicochemical properties of these ionic liquids can easily be altered by making the different combinations of amino acids as anion along with possible cation modification which makes amino acid ionic liquids more suitable to understand the different kinds of molecular and ionic interactions with sufficient depth so that they can provide fruitful information for a molecular level understanding of more complicated biological processes. In this context, volumetric and osmotic coefficient measurements for aqueous solutions containing 1-ethyl-3-methylimidazolium ([Emim]) based amino acid ionic liquids of glycine, alanine, valine, leucine, and isoleucine are reported at 298.15 K. From experimental osmotic coefficient data, mean molal activity coefficients of ionic liquids were estimated and analyzed using the Debye-Hückel and Pitzer models. The hydration numbers of ionic liquids in aqueous solutions were obtained using activity data. Pitzer ion interaction parameters are estimated and compared with other electrolytes reported in the literature. The nonelectrolyte contribution to the aqueous solutions containing ionic liquids was studied by calculating the osmotic second virial coefficient through an application of the McMillan-Mayer theory of solution. It has been found that the second osmotic virial coefficient which includes volume effects correlates linearly with the Pitzer ion interaction parameter estimated independently from osmotic data as well as the hydrophobicity of ionic liquids. The enthalpy-entropy compensation effect, explained using the Starikov-Nordén model of enthalpy-entropy compensation, and partial molar entropy analysis for aqueous [Emim][Gly] solutions are made by using experimental Gibb

  17. Development of Ionic Liquid Monopropellants for In-Space Propulsion

    NASA Technical Reports Server (NTRS)

    Blevins, John A.; Osborne, Robin; Drake, Gregory W.

    2005-01-01

    A family of new, low toxicity, high energy monopropellants is currently being evaluated at NASA Marshall Space Flight Center for in-space rocket engine applications such as reaction control engines. These ionic liquid monopropellants, developed in recent years by the Air Force Research Laboratory, could offer system simplification, less in-flight thermal management, and reduced handling precautions, while increasing propellant energy density as compared to traditional storable in-space propellants such as hydrazine and nitrogen tetroxide. However, challenges exist in identifying ignition schemes for these ionic liquid monopropellants, which are known to burn at much hotter combustion temperatures compared to traditional monopropellants such as hydrazine. The high temperature combustion of these new monopropellants make the use of typical ignition catalyst beds prohibitive since the catalyst cannot withstand the elevated temperatures. Current research efforts are focused on monopropellant ignition and burn rate characterization, parameters that are important in the fundamental understanding of the monopropellant behavior and the eventual design of a thruster. Laboratory studies will be conducted using alternative ignition techniques such as laser-induced spark ignition and hot wire ignition. Ignition delay, defined as the time between the introduction of the ignition source and the first sign of light emission from a developing flame kernel, will be measured using Schlieren visualization. An optically-accessible liquid monopropellant burner will be used to determine propellant burn rate as a function of pressure and initial propellant temperature. The burn rate will be measured via high speed imaging through the chamber s windows.

  18. 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.

  19. Gelatin-ionic liquid based platform for glucose detection.

    PubMed

    Sharma, Anshu; Rawat, Kamla; Solanki, Pratima R; Bohidar, H B

    2015-01-01

    Herein, we have fabricated a novel platform consisting of gelatin B in ionic liquid [1-ethyl- 3-methylimidazolium chloride [C2mim][Cl] (ionic liquid, IL)] formed ionogels (Ig) by dissolution method and used it for glucose detection. The ionogels were deposited onto indium tin oxide (ITO) coated glass plate using drop casting technique. Glucose oxidase (GOx) was selected as a model enzyme to investigate its interaction with Ig/ITO electrode using electrochemical and optical methods. Structural and morphological studies of the Ig/ITO electrode were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and cyclic voltmmetry before and after GOx immobilization. It was found that [C2mim][Cl] enhanced electrocatalytic behaviour of the fabricated electrode which provided electron transfer rate constant as Ks ≈ 0.113 s(-1). Response study of GOx/Ig/ITO bioelectrode as a function of glucose concentration was monitored. These gelatin-ionic liquid based bioelectrodes showed following results obtained from electrochemical technique linearity ≈ 1-20 mM, and low value of Michaelis-Menten constant, Km ≈ 0.174 mM with sensitivity ≈ 4.6µA mM(-1) cm(-2). In contrast, the optical detection of glucose exhibited linearity in the range of 6-20 mM, value of Km ≈ 3.8 mM with sensitivity 6.76 x 10(-3) Abs/mM cm(2). This clearly indicated that the prepared ionogel based electrodes will provide a promising platform for glucose detection. PMID:25858131

  20. Li(+) solvation in glyme-Li salt solvate ionic liquids.

    PubMed

    Ueno, Kazuhide; Tatara, Ryoichi; Tsuzuki, Seiji; Saito, Soshi; Doi, Hiroyuki; Yoshida, Kazuki; Mandai, Toshihiko; Matsugami, Masaru; Umebayashi, Yasuhiro; Dokko, Kaoru; Watanabe, Masayoshi

    2015-03-28

    Certain molten complexes of Li salts and solvents can be regarded as ionic liquids. In this study, the local structure of Li(+) ions in equimolar mixtures ([Li(glyme)]X) of glymes (G3: triglyme and G4: tetraglyme) and Li salts (LiX: lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]), lithium bis(pentafluoroethanesulfonyl)amide (Li[BETI]), lithium trifluoromethanesulfonate (Li[OTf]), LiBF4, LiClO4, LiNO3, and lithium trifluoroacetate (Li[TFA])) was investigated to discriminate between solvate ionic liquids and concentrated solutions. Raman spectra and ab initio molecular orbital calculations have shown that the glyme molecules adopt a crown-ether like conformation to form a monomeric [Li(glyme)](+) in the molten state. Further, Raman spectroscopic analysis allowed us to estimate the fraction of the free glyme in [Li(glyme)]X. The amount of free glyme was estimated to be a few percent in [Li(glyme)]X with perfluorosulfonylamide type anions, and thereby could be regarded as solvate ionic liquids. Other equimolar mixtures of [Li(glyme)]X were found to contain a considerable amount of free glyme, and they were categorized as traditional concentrated solutions. The activity of Li(+) in the glyme-Li salt mixtures was also evaluated by measuring the electrode potential of Li/Li(+) as a function of concentration, by using concentration cells against a reference electrode. At a higher concentration of Li salt, the amount of free glyme diminishes and affects the electrode reaction, leading to a drastic increase in the electrode potential. Unlike conventional electrolytes (dilute and concentrated solutions), the significantly high electrode potential found in the solvate ILs indicates that the solvation of Li(+) by the glyme forms stable and discrete solvate ions ([Li(glyme)](+)) in the molten state. This anomalous Li(+) solvation may have a great impact on the electrode reactions in Li batteries. PMID:25733406

  1. Nanostructure of the Ionic Liquid-Graphite Stern Layer.

    PubMed

    Elbourne, Aaron; McDonald, Samila; Voïchovsky, Kislon; Endres, Frank; Warr, Gregory G; Atkin, Rob

    2015-07-28

    Ionic liquids (ILs) are attractive solvents for devices such as lithium ion batteries and capacitors, but their uptake is limited, partially because their Stern layer nanostructure is poorly understood compared to molecular solvents. Here, in situ amplitude-modulated atomic force microscopy has been used to reveal the Stern layer nanostructure of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm TFSI)-HOPG (highly ordered pyrolytic graphite) interface with molecular resolution. The effect of applied surface potential and added 0.1 wt/wt % Li TFSI or EMIm Cl on ion arrangements is probed between ±1 V. For pure EMIm TFSI at open-circuit potential, well-defined rows are present on the surface formed by an anion-cation-cation-anion (A-C-C-A) unit cell adsorbed with like ions adjacent. As the surface potential is changed, the relative concentrations of cations and anions in the Stern layer respond, and markedly different lateral ion arrangements ensue. The changes in Stern layer structure at positive and negative potentials are not symmetrical due to the different surface affinities and packing constraints of cations and anions. For potentials outside ±0.4 V, images are featureless because the compositional variation within the layer is too small for the AFM tip to detect. This suggests that the Stern layer is highly enriched in either cations or anions (depending on the potential) oriented upright to the surface plane. When Li(+) or Cl(-) is present, some Stern layer ionic liquid cations or anions (respectively) are displaced, producing starkly different structures. The Stern layer structures elucidated here significantly enhance our understanding of the ionic liquid electrical double layer. PMID:26051040

  2. Coordinating Chiral Ionic Liquids: Design, Synthesis, and Application in Asymmetric Transfer Hydrogenation under Aqueous Conditions

    PubMed Central

    Vasiloiu, Maria; Gaertner, Peter; Zirbs, Ronald; Bica, Katharina

    2015-01-01

    Hydrophilic coordinating chiral ionic liquids with an amino alcohol substructure were developed and efficiently applied to the asymmetric reduction of ketones. Their careful design and adaptability to the desired reaction conditions allow for these chiral ionic liquids to be used as the sole source of chirality in a ruthenium-catalyzed transfer hydrogenation reaction of aromatic ketones. When used in this reaction system, these chiral ionic liquids afforded excellent yields and high enantioselectivities. PMID:26279638

  3. Radiation-induced intermediates in irradiated glassy ionic liquids at low temperature

    NASA Astrophysics Data System (ADS)

    Saenko, Elizaveta V.; Lukianova, Mariia A.; Shiryaeva, Ekaterina S.; Takahashi, Kenji; Feldman, Vladimir I.

    2016-07-01

    The primary radiation-induced processes in irradiated low-temperature pyrrolidinium- and piperidinium-type ionic liquids were investigated by EPR and optical absorption spectroscopy. A narrow singlet signal in the EPR spectra of irradiated ionic liquids was attributed to the physically stabilized electron. Broad absorption band in visible region was ascribed to "hole" species. Aromatic scavengers react with "hole" species in glassy irradiated ionic liquids at 77 K.

  4. NMR Characterization of Ionicity and Transport Properties for a Series of Diethylmethylamine Based Protic Ionic Liquids.

    PubMed

    Davidowski, Stephen K; Thompson, Forrest; Huang, Wei; Hasani, Mohammad; Amin, Samrat A; Angell, C Austen; Yarger, Jeffery L

    2016-05-12

    The ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing nuclear magnetic resonance (NMR) spectroscopy. PILs were formed via the protonation of DEMA by an array of acids spanning a large range of acidities. A correlation between the (1)H chemical shift of the exchangeable proton and the acidity of the acid used for the synthesis of the PIL was observed. The gas phase proton affinity of the acid was found to be a better predictor of the extent of proton transfer than the commonly used aqueous ΔpKa. Pulsed field gradient (PFG) NMR was used to determine the diffusivity of the exchangeable proton in a subset of the PILs. The exchangeable proton diffuses with the acid if the PIL is synthesized with a weak acid, and with the base if a strong acid is used. The ionicity of the PILs was characterized using the Walden analysis and by comparing to the ideal Nernst-Einstein conductivity predicted from the (1)H PFG-NMR results. PMID:27088704

  5. Development of ionic gels using thiol-based monomers in ionic liquid

    NASA Astrophysics Data System (ADS)

    Ahmed, Kumkum; Naga, Naofumi; Kawakami, Masaru; Furukawa, Hidemitsu

    2016-04-01

    Ionic gels (IGs) using ionic liquids (ILs) can propose diverse applications in the field of optics, sensors and separation have opened wide prospects in materials science. ILs have attracted remarkable interest for gel polymer electrolytes and batteries based on their useful properties such as non-volatility, non-flammability, a wide electrochemical window, high thermal stability and a high ionic conductivity. The formation of gel in IL media makes it possible to immobilize ILs within organic or inorganic matrices and to take advantage of their unique properties in the solid state, thus eliminating some shortcomings related to shaping and risk of leakage. In this work for the first time we used multifunctional thiol monomers having uniform structure and good compatibility with the IL of our interest. Therefore we focused on developing thiol monomer-based IGs using multifunctional thiol monomers and acrylate crosslinkers utilizing thiol-ene reaction between monomer and crosslinking molecules in an IL medium and characterize their physico-chemical properties like thermal, conductive, mechanical properties etc.. This work has been focused mainly to improve the mechanical strength of IGs and make prospects of IGs in tribology and lubricants.

  6. Fluorescence of fullerene C 70 in ionic liquids

    NASA Astrophysics Data System (ADS)

    Martins, Sofia; Fedorov, Aleksander; Afonso, Carlos A. M.; Baleizão, Carlos; Berberan-Santos, Mário N.

    2010-09-01

    It is shown that pristine fullerene C 70 can be solubilised in imidazolium, ammonium and phosphonium based ionic liquids (ILs) bearing long alkyl chains (C 8 or higher). The absorption and fluorescence properties are similar to those displayed in conventional polar solvents except in ILs containing chloride as the counter ion, which completely quench the fluorescence of C 70. Fluorescence decay analysis using a sum of Becquerel functions to account for the complex decay of background emission allows the successful recovery of the solute's lifetime.

  7. Rapid Preparation of Silsesquioxane-Based Ionic Liquids.

    PubMed

    Li, Liguo; Liu, Hongzhi

    2016-03-24

    Three new hybrid ionic liquids (ILs) based on cage silsesquioxane (SQ) were rapidly prepared in high yields from octa(mercaptopropyl)silsesquioxane and 1-allyl-3-methylimidazolium salts (Br(-) , BF4 (-) , PF6 (-) ) through the photochemical thiol-ene reaction. These SQ-based ILs exhibited low glass transition temperatures and good thermal stability. The unique amphiphilic nature of these hybrid ILs cause them to self-assemble into perfect vesicles with "yolk-shell" structures, in which cages formed the "yolk" due to their aggregation and outer anions formed the "shell". PMID:26864313

  8. Doubly thermo-responsive copolymers in ionic liquid.

    PubMed

    Nguyen, H H; El Ezzi, M; Mingotaud, C; Destarac, M; Marty, J-D; Lauth-de Viguerie, N

    2016-04-01

    We report the behaviour of thermoresponsive block copolymers of n-butyl acrylate and N-alkyl acrylamides in [C2mim][NTf2]. Poly(N-isopropylacrylamide) exhibits an upper critical solution temperature in [C2mim][NTf2] whereas poly(n-butyl acrylate) has a lower critical solution temperature. Consequently, these polymers exhibit double thermo-responsiveness correlated with the macromolecular structure. Moreover, a switching from micellar to reverse micellar structures was induced by a change in temperature. This property enables the development of reversible shuttles between ionic liquids and water. PMID:26931173

  9. Synthesis of cellulose methylcarbonate in ionic liquids using dimethylcarbonate.

    PubMed

    Labafzadeh, Sara R; Helminen, K Juhani; Kilpeläinen, Ilkka; King, Alistair W T

    2015-01-01

    Dialkylcarbonates are viewed as low-cost, low-toxicity reagents, finding application in many areas of green chemistry. Homogeneous alkoxycarbonylation of cellulose was accomplished by applying dialkycarbonates (dimethyl and diethyl carbonate) in the ionic liquid-electrolyte trioctylphosphonium acetate ([P8881 ][OAc])/DMSO or 1-ethyl-3-methylimidazolium acetate ([emim][OAc]). Cellulose dialkylcarbonates with a moderate degree of substitution (DS∼1) are accessible via this procedure and cellulose methylcarbonate was thoroughly characterized for its chemical and physical properties after regeneration. This included HSQC & HMBC NMR, ATR-IR, molecular weight distribution, morphology, thermal properties, and barrier properties after film formation. PMID:25378289

  10. Regenerating cellulose from ionic liquids for an accelerated enzymatic hydrolysis

    SciTech Connect

    Zhao, Hua; Jones, Cecil L; Baker, Gary A; Xia, Shuqian; Olubajo, Olarongbe; Person, Vernecia

    2009-01-01

    The efficient conversion of lignocellulosic materials into fuel ethanol has become a research priority in producing affordable and renewable energy. The pretreatment of lignocelluloses is known to be key to the fast enzymatic hydrolysis of cellulose. Recently, certain ionic liquids (ILs)were found capable of dissolving more than 10 wt% cellulose. Preliminary investigations [Dadi, A.P., Varanasi, S., Schall, C.A., 2006. Enhancement of cellulose saccharification kinetics using an ionic liquid pretreatment step. Biotechnol. Bioeng. 95, 904 910; Liu, L., Chen, H., 2006. Enzymatic hydrolysis of cellulose materials treated with ionic liquid [BMIM]Cl. Chin. Sci. Bull. 51, 2432 2436; Dadi, A.P., Schall, C.A., Varanasi, S., 2007. Mitigation of cellulose recalcitrance to enzymatic hydrolysis by ionic liquid pretreatment. Appl. Biochem. Biotechnol. 137 140, 407 421] suggest that celluloses regenerated from IL solutions are subject to faster saccharification than untreated substrates. These encouraging results offer the possibility of using ILs as alternative and nonvolatile solvents for cellulose pretreatment. However, these studies are limited to two chloride-based ILs: (a) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), which is a corrosive, toxic and extremely hygroscopic solid (m.p. 70 C), and (b) 1-allyl-3-methylimidazolium chloride ([AMIM]Cl), which is viscous and has a reactive side-chain. Therefore, more in-depth research involving other ILs is much needed to explore this promising pretreatment route. For this reason, we studied a number of chloride- and acetate-based ILs for cellulose regeneration, including several ILs newly developed in our laboratory. This will enable us to select inexpensive, efficient and environmentally benign solvents for processing cellulosic biomass. Our data confirm that all regenerated celluloses are less crystalline (58 75% lower) and more accessible to cellulase (>2 times) than untreated substrates. As a result, regenerated Avicel

  11. Useful halophilic, thermostable and ionic liquids tolerant cellulases

    DOEpatents

    Zhang, Tao; Datta, Supratim; Simmons, Blake A.; Rubin, Edward M.

    2016-06-28

    The present invention provides for an isolated or recombinant polypeptide comprising an amino acid sequence having at least 70% identity with the amino acid sequence of a Halorhabdus utahensis cellulase, such as Hu-CBH1, wherein said amino acid sequence has a halophilic thermostable and/or thermophilic cellobiohydrolase (CBH) activity. In some embodiments, the polypeptide has a CBH activity that is resistant to up to about 20% of ionic liquids. The present invention also provides for compositions comprising and methods using the isolated or recombinant polypeptide.

  12. Hydrogen fluoride capture by imidazolium acetate ionic liquid

    NASA Astrophysics Data System (ADS)

    Chaban, Vitaly

    2015-04-01

    Extraction of hydrofluoric acid (HF) from oils is a drastically important problem in petroleum industry, since HF causes quick corrosion of pipe lines and brings severe health problems to humanity. Some ionic liquids (ILs) constitute promising scavenger agents thanks to strong binding to polar compounds and tunability. PM7-MD simulations and hybrid density functional theory are employed here to consider HF capture ability of ILs. Discussing the effects and impacts of the cation and the anion separately and together, we evaluate performance of imidazolium acetate and outline systematic search guidelines for efficient adsorption and extraction of HF.

  13. Influence of the ionic liquid cation on the solvent extraction of trivalent rare-earth ions by mixtures of Cyanex 923 and ionic liquids.

    PubMed

    Rout, Alok; Binnemans, Koen

    2015-01-21

    Trivalent rare-earth ions were extracted from nitric acid medium by the neutral phosphine oxide extractant Cyanex 923 into ionic liquid phases containing the bis(trifluoromethylsulfonyl)imide anion. Five different cations were considered: 1-butyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, methyltributylammonium, methyltrioctylammonium and trihexyl(tetradecyl)phosphonium. The extraction behavior of neodymium(iii) was investigated as a function of various parameters: pH, extractant concentration, concentration of the neodymium(iii) ion in the aqueous feed and concentration of the salting-out agent. The loading capacity of the ionic liquid phase was studied. The extraction efficiency increased with increasing pH of the aqueous feed solution. The extraction occurred for all ionic liquids via an ion-exchange mechanism and the extraction efficiency could be related to the solubility of the ionic liquid cation in the aqueous phase: high distribution ratios for hydrophilic cations and low ones for hydrophobic cations. Addition of nitrate ions to the aqueous phase resulted in an increase in extraction efficiency for ionic liquids with hydrophobic cations due to extraction of neutral complexes. Neodymium(iii) could be stripped from the ionic liquid phase by 0.5-1.0 M nitric acid solutions and the extracting phase could be reused. The extractability of other rare earths present in the mixture was compared for the five ionic liquids. PMID:25423581

  14. Dispelling some myths about the CO2 solubility in ionic liquids.

    PubMed

    Carvalho, P J; Kurnia, K A; Coutinho, J A P

    2016-06-01

    Ionic liquids have been objects of extensive research for physical sorption of CO2 and a number of myths have been perpetuated in the literature, for lack of a critical analysis, concerning their potential for CO2 capture. This study carries a critical analysis of a number of widely accepted ideas and others not so well accepted that have been repeatedly expressed in the literature concerning the CO2 physical sorption in ionic liquids. Using the CO2 solubility in eicosane as benchmark, it will be shown that there is no evidence that ILs display a physical sorption of CO2 larger than n-alkanes when analyzed in adequate concentration units; the fluorination of the ions has no impact on the CO2 solubility and the oxygenation will marginally contribute to a decrease of the solubility. Ionic liquid-based deep eutectic systems are also shown to have a poor CO2 solubility. Although these widely used approaches to physically enhance the CO2 solubility in ILs do not seem to have any positive influence, this does not mean that other types of interaction cannot provide enhanced CO2 solubility as in the case of the anion [B(CN)4] confirmed here by a critical analysis of the published data. The mechanism of CO2 physical sorption in ionic liquids is discussed based on the results analyzed, supported by spectroscopic measurements and molecular simulations previously reported and further suggestions of possibilities for enhanced physical sorption based on fluorinated aromatic rings, other cyano based anions, mixtures with other ILs or solvents or the use of porous liquids are proposed. PMID:27189669

  15. Understanding positive and negative deviations in polarity of ionic liquid mixtures by pseudo-solvent approach.

    PubMed

    Beniwal, Vijay; Kumar, Anil

    2016-08-24

    Physico-chemical properties of liquid mixtures in general display large deviations from linear behaviour, arising out of complex specific and non-specific intermolecular interactions. The polarity of liquid mixtures displaying large positive and negative deviations can be minimized and linear mixing can be achieved in liquids using a pseudo-solvent methodology. The work described herein is designed to investigate the influence of different physical parameters on the linear pseudo-solvent composition in ionic liquid mixtures. For this purpose, we have determined the deviations from linearity, ΔE values (defined as given by ) for binary mixtures of a variety of ionic liquids, including two molecular solvents, DMSO and formamide. Firstly, the investigations were carried out in three 1-butyl-3-methylimidazolium cation based aprotic ionic liquids and the roles of anionic structure and hydrogen bond acceptor basicities (β values) of the ionic liquids were determined. The influence of the cationic structure, i.e., the hydrogen bond donor acidity (α values) and non-associative nature of the ionic liquids, was determined using C2-methylated analogs, 1-butyl-2,3-dimethylimidazolium cation based ionic liquids. The role of the protic nature of ionic liquids was studied in two protic ionic liquids, viz., 1-methylimidazolium formate and 1-methylimidazolium acetate. The effects of the temperature, pseudo-solvent structure and solvatochromic probe structure on the ΔE values were also explored. PMID:27523572

  16. Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

    PubMed

    de Eulate, Eva Alvarez; Silvester, Debbie S; Arrigan, Damien W M

    2015-12-01

    At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents. PMID:26489692

  17. Methods of using ionic liquids having a fluoride anion as solvents

    DOEpatents

    Pagoria, Philip; Maiti, Amitesh; Gash, Alexander; Han, Thomas Yong; Orme, Christine; Fried, Laurence

    2011-12-06

    A method in one embodiment includes contacting a strongly hydrogen bonded organic material with an ionic liquid having a fluoride anion for solubilizing the strongly hydrogen bonded organic material; and maintaining the ionic liquid at a temperature of about 90.degree. C. or less during the contacting. A method in another embodiment includes contacting a strongly hydrogen bonded organic material with an ionic liquid having an acetate or formate anion for solubilizing the strongly hydrogen bonded organic material; and maintaining the ionic liquid at a temperature of less than about 90.degree. C. during the contacting.

  18. The Effect of Ionic Liquids on Protein Crystallization and X-ray Diffraction Resolution

    SciTech Connect

    Judge, Russell A.; Takahashi, Sumiko; Longenecker, Kenton L.; Fry, Elizabeth H.; Abad-Zapatero, Cele; Chiu, Mark L.

    2009-09-08

    Ionic liquids exhibit a variety of properties that make them attractive solvents for biomaterials. Given the potential for productive interaction between ionic liquids and biological macromolecules, we investigated the use of ionic liquids as precipitating agents and additives for protein crystallization for six model proteins (lysozyme, catalase, myoglobin, trypsin, glucose isomerase, and xylanase). The ionic liquids produced changes in crystal morphology and mediated significant increases in crystal size in some cases. Crystals grown using ionic liquids as precipitating agents or as additives provided X-ray diffraction resolution similar to or better than that obtained without ionic liquids. Based upon the experiments performed with model proteins, the ionic liquids were used as additives for the crystallization of the poorly diffracting monoclonal antibody 106.3 Fab in complex with the B-type natriuretic peptide (5-13). The ionic liquids improved the crystallization behavior and provided improved diffraction resulting in the determination of the structure. Ionic liquids should be considered as useful additives for the crystallization of other proteins.

  19. Design and Evaluation of Ionic Liquids as Novel CO2 Absorbents

    SciTech Connect

    Edward Maginn

    2007-07-15

    This is the final report for project DE-FG26-04NT42122 'Design and Evaluation of Ionic Liquids as Novel CO{sub 2} Absorbents'. The objective of this 'breakthrough concepts' project was to investigate the feasibility of using ionic liquids for post-combustion CO{sub 2} capture and obtain a fundamental understanding of the solubility of CO{sub 2} and other components present in flue gas in ionic liquids. Our plan was to obtain information on how composition and structure of ionic liquid molecules affected solubility and other important physical properties via two major efforts: synthesis and experimental measurements and molecular simulation. We also planned to perform preliminary systems modeling study to assess the economic viability of a process based on ionic liquids. We accomplished all the milestones and tasks specified in the original proposal. Specifically, we carried out extensive quantum and classical atomistic-level simulations of a range of ionic liquids. These calculations provided detailed information on how the chemical composition of ionic liquids affects physical properties. We also learned important factors that govern CO{sub 2} solubility. Using this information, we synthesized or acquired 33 new ionic liquids. Many of these had never been made before. We carried out preliminary tests on all of these compounds, and more extensive tests on those that looked most promising for CO{sub 2} capture. We measured CO{sub 2} solubility in ten of these ionic liquids. Through our efforts, we developed an ionic liquid that has a CO{sub 2} solubility 2.6 times greater than the 'best' ionic liquid available to us at the start of the project. Moreover, we demonstrated that SO{sub 2} is also extremely soluble in ionic liquids, opening up the possibility of using ionic liquids to remove both SO{sub 2} and CO{sub 2} from flue gas. In collaboration with Trimeric Inc., a preliminary systems analysis was conducted and the results used to help identify physical

  20. Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

    PubMed

    Yu, Honglian; Merib, Josias; Anderson, Jared L

    2016-03-18

    Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. PMID:26896916

  1. Oxygen Production from Lunar Regolith using Ionic Liquids

    NASA Technical Reports Server (NTRS)

    Paley, Mark Steven; Karr, Laurel J.; Curreri, Peter

    2009-01-01

    The objective of this work and future follow-on work is to develop a safe, efficient, and recyclable method for oxygen and/or metals extraction from lunar regolith, in support of establishing a manned lunar outpost. The approach is to solubilize the oxides that comprise lunar regolith in media consisting of ionic liquids (ILs) and/or their mixtures at temperatures at or below 300 C. Once in solution, electrolysis can either be performed in-situ to generate oxygen at the anode and hydrogen and/or metals (silicon, iron, aluminum, titanium, etc.) at the cathode. Alternatively, the water that is generated during the solubilization process can be distilled out and condensed into a separate IL and then electrolysized to produce hydrogen and oxygen. In the case of lunar regolith, this method could theoretically produce 44g oxygen per 100g of regolith. The oxygen can be used for human life support and/or as an oxidizer for rocket fuels, and the metals can be used as raw materials for construction and/or device fabrication. Moreover, the hydrogen produced can be used to re-generate the acidic medium, which can then be used to process additional regolith, thereby making the materials recyclable and limiting upmass requirements. An important advantage of IL acid systems is that they are much "greener" and safer than conventional materials used for regolith processing such as sulfuric or hydrochloric acids. They have very low vapor pressures, which means that they contain virtually no toxic and/or flammable volatile content, they are relatively non-corrosive, and they can exhibit good stability in harsh environments (extreme temperatures, hard vacuum, etc.). Furthermore, regolith processing can be achieved at lower temperatures than other processes such as molten oxide electrolysis or hydrogen reduction, thereby reducing initial power requirements. Six ILs have been synthesized and tested for their capability to dissolve lunar simulant, and for electrochemical and thermal

  2. Redox-active cross-linkable poly(ionic liquid)s.

    PubMed

    Sui, Xiaofeng; Hempenius, Mark A; Vancso, G Julius

    2012-03-01

    The synthesis of a new class of cross-linkable redox-responsive poly(ferrocenylsilane)-based poly(ionic liquid)s (PFS-PILs) is reported. PFS-PILs self-cross-link at low concentrations into nanogels or form macroscopic hydrogel networks at higher concentrations. PFS-PILs proved to be efficient dispersants in the microemulsion polymerization of methyl methacrylate, producing stable PFS-poly(methyl methacrylate) latex suspensions. PMID:22353019

  3. Fast Measurement of Methanol Concentration in Ionic Liquids by Potential Step Method

    PubMed Central

    Hainstock, Michael L.; Tang, Yijun

    2015-01-01

    The development of direct methanol fuel cells required the attention to the electrolyte. A good electrolyte should not only be ionic conductive but also be crossover resistant. Ionic liquids could be a promising electrolyte for fuel cells. Monitoring methanol was critical in several locations in a direct methanol fuel cell. Conductivity could be used to monitor the methanol content in ionic liquids. The conductivity of 1-butyl-3-methylimidazolium tetrafluoroborate had a linear relationship with the methanol concentration. However, the conductivity was significantly affected by the moisture or water content in the ionic liquid. On the contrary, potential step could be used in sensing methanol in ionic liquids. This method was not affected by the water content. The sampling current at a properly selected sampling time was proportional to the concentration of methanol in 1-butyl-3-methylimidazolium tetrafluoroborate. The linearity still stood even when there was 2.4 M water present in the ionic liquid. PMID:25802522

  4. Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

    DOE PAGESBeta

    Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang; Meisner, Roberta A.; Luo, Huimin; Delmau, Lætitia H.; Dai, Sheng; Moyer, Bruce A.

    2016-05-19

    A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO3 to UO2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

  5. Determination of rifaximin in rat serum by ionic liquid based dispersive liquid-liquid microextraction combined with RP-HPLC.

    PubMed

    Rao, Ramisetti Nageswara; Vali, Rajavarapu Mastan; Rao, Alamanda Vara Prasada

    2012-08-01

    An efficient and environmental friendly ionic liquid based dispersive liquid-liquid microextraction procedure was optimized for determination of rifaximin in rat serum by reverse phase high-performance liquid chromatography. The effect of ionic liquids, dispersive solvents, extractant/disperser ratio, and salt concentrations on sample recovery and enrichment factors were studied. Among the five ionic liquids studied in the present investigation, 1-butyl-3-methylimidazolium hexafluorophosphate was found to be most effective for extraction of rifaximin. The recovery was found to be more than 98% using 1-butyl-3-methylimidazolium hexafluorophosphate and methanol as extraction and dispersive solvents, at an extractant/disperser ratio of 0.43. The recovery was further enhanced to 99.5% by the addition of 5.0% NaCl solution. A threefold enhancement in detection limit was achieved when compared to protein precipitation. The ionic liquid containing the extracted rifaximin was directly injected into HPLC system. The linear relationship was observed in the range of 0.03-10.0 μg/mL with the correlation coefficient (r(2)) 0.9998. Limits of detection and quantification were found to be 0.01 and 0.03 μg/mL, respectively. The relative standard deviation was 2.5%. The method was validated and applied to study pharmacokinetics of rifaxmin in rat serum. PMID:22753340

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

    PubMed

    Ghoufi, Aziz; Szymczyk, Anthony; Malfreyt, Patrice

    2016-01-01

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

  7. Furfural production from Eucalyptus wood using an Acidic Ionic Liquid.

    PubMed

    Peleteiro, Susana; Santos, Valentín; Garrote, Gil; Parajó, Juan Carlos

    2016-08-01

    Eucalyptus globulus wood samples were treated with hot, compressed water to separate hemicelluloses (as soluble saccharides) from a solid phase mainly made up of cellulose and lignin. The liquid phase was dehydrated, and the resulting solids (containing pentoses as well as poly- and oligo- saccharides made up of pentoses) were dissolved and reacted in media containing an Acidic Ionic Liquid (1-butyl-3-methylimidazolium hydrogen sulfate) and a co-solvent (dioxane). The effects of the reaction time on the product distribution were studied at temperatures in the range 120-170°C for reaction times up to 8h, and operational conditions leading to 59.1% conversion of the potential substrates (including pentoses and pentose structural units in oligo- and poly- saccharides) into furfural were identified. PMID:27112846

  8. Controlled electrodeposition of Au monolayer film on ionic liquid

    NASA Astrophysics Data System (ADS)

    Ma, Qiang; Pang, Liuqing; Li, Man; Zhang, Yunxia; Ren, Xianpei; Liu, Shengzhong Frank

    2016-05-01

    Gold (Au) nanoparticles have been attractive for centuries for their vibrant appearance enhanced by their interaction with sunlight. Nowadays, there have been tremendous research efforts to develop them for high-tech applications including therapeutic agents, sensors, organic photovoltaics, medical applications, electronics and catalysis. However, there remains to be a challenge to fabricate a monolayer Au coating with complete coverage in controlled fashion. Here we present a facile method to deposit a uniform Au monolayer (ML) film on the [BMIM][PF6] ionic liquid substrate using an electrochemical deposition process. It demonstrates that it is feasible to prepare a solid phase coating on the liquid-based substrate. Moreover, the thickness of the monolayer coating can be controlled to a layer-by-layer accuracy.

  9. Ultrafast diffusion of Ionic Liquids Confined in Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Ghoufi, Aziz; Szymczyk, Anthony; Malfreyt, Patrice

    2016-06-01

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

  10. Ultrafast diffusion of Ionic Liquids Confined in Carbon Nanotubes

    PubMed Central

    Ghoufi, Aziz; Szymczyk, Anthony; Malfreyt, Patrice

    2016-01-01

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

  11. Tailored ionic liquid-based surfactants for the formation of microemulsions with water and a hydrophobic ionic liquid.

    PubMed

    Porada, Jan H; Zauser, Diana; Feucht, Birgit; Stubenrauch, Cosima

    2016-08-14

    Microemulsions (μe) with water and a hydrophobic ionic liquid (IL) usually require 45-60 wt% surfactant to solubilize equal amounts of water and IL. To increase the efficiency we designed a new class of surfactants by combining a hydrophilic but IL-ophobic carbohydrate-based part with a hydrophobic but IL-ophilic IL-based part. These surfactants allow formulating microemulsions with 20 wt% surfactant only which opens up a new arena for efficient water-IL μes. PMID:27405741

  12. Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity

    SciTech Connect

    Miranda, Daniel F.; Urata, Chihiro; Masheder, Benjamin; Dunderdale, Gary J.; Hozumi, Atsushi; Yagihashi, Makoto

    2014-05-01

    A fluorinated and hydrophobic ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, effectively served as an advantageous lubricating liquid for the preparation of physically and chemically stable omniphobic surfaces based on slippery liquid-infused porous surfaces. Here, we used particulate microstructures as supports, prepared by the chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent surface modification with (3-aminopropyl)triethoxysilane. Confirmed by SEM and contact angle measurements, the resulting IL-infused microtextured surfaces are smooth and not only water but also various low surface tension liquids can easily slide off at low substrate tilt angles of <5°, even after exposure to high temperature, vacuum, and UV irradiation.

  13. Development of Ionic Liquid Monopropellants for In-Space Propulsion

    NASA Technical Reports Server (NTRS)

    Blevins, John A.; Drake, Gregory W.; Osborne, Robin J.

    2005-01-01

    A family of new, low toxicity, high energy monopropellants is currently being evaluated at NASA Marshall Space Flight Center for in-space rocket engine applications such as reaction control engines. These ionic liquid monopropellants, developed in recent years by the Air Force Research Laboratory, could offer system simplification, less in-flight thermal management, and reduced handling precautions, while increasing propellant energy density as compared to traditional storable in-space propellants such as hydrazine and nitrogen tetroxide. However, challenges exist in identifying ignition schemes for these ionic liquid monopropellants, which are known to burn at much hotter combustion temperatures compared to traditional monopropellants such as hydrazine. The high temperature combustion of these new monopropellants make the use of typical ignition catalyst beds prohibitive since the catalyst cannot withstand the elevated temperatures. Current research efforts are focused on monopropellant ignition and burn rate characterization, parameters that are important in the fundamental understanding of the monopropellant behavior and the eventual design of a thruster. Laboratory studies will be conducted using alternative ignition techniques such as laser-induced spark ignition and hot wire ignition. Ignition delay, defined as the time between the introduction of the ignition source and the first sign of light emission from a developing flame kernel, will be measured using Schlieren visualization. An optically-accessible liquid monopropellant burner, shown schematically in Figure 1 and similar in design to apparatuses used by other researchers to study solid and liquid monopropellants, will be used to determine propellant burn rate as a function of pressure and initial propellant temperature. The burn rate will be measured via high speed imaging through the chamber s windows.

  14. A computational approach to design energetic ionic liquids.

    PubMed

    Singh, Hari Ji; Mukherjee, Uttama

    2013-06-01

    The present work deals with the theoretical estimation of ion-pair binding energies and the energetic properties of four ion pairs formed by combining the 1-butyl-2,4-dinitro-3-methyl imidazolium ion with nitrate (I), perchlorate (II), dinitramide (III), or 3,5-dinitro-1,2,4-triazolate (IV) anions. The counterpoise-corrected ion-pair binding energies were calculated for each ion pair at the B3LYP/6-311+G(d,p) level of theory. Results show that the cation-anion interaction is strongest for ion pair I and weakest for IV, indicating that the nitrate (I) has a greater tendency to exist as a stable ionic salt whereas the 3,5-dinitro-1,2,4-triazolate (IV) may exist as an ionic liquid. Natural bond orbital (NBO) analysis and electrostatic potential (ESP) mapping revealed that charge transfer occurs in all of the ion pairs, but is greatest (0.25e) for ion pair I and smallest (0.03e) for IV, resulting in ion pair I being the least polarized. A nucleus-independent chemical shift (NICS) study revealed that the aromaticity of the 1-butyl-2,4-dinitro-3-methyl imidazolium ion significantly increases in ion pair IV, indicating that this has the greatest charge delocalization among all of the four ion pairs considered. Studies of thermodynamic and detonation properties showed that ion pair II is the most energetic ion pair in terms of its detonation velocity (D = 7.5 km s(-1)) and detonation pressure (P = 23.1 GPa). It is also envisaged that ion pair IV would exist as an energetic azolium azolate type ionic liquid that could be conveniently used as a secondary explosive characterized by detonation parameters D and P of 6.9 km s(-1) and 19.3 GPa, respectively. These values are comparable to those of conventional explosives such as TNT. PMID:23392764

  15. Ionic Liquid Induced Band Shift of Titanium Dioxide.

    PubMed

    Weber, Henry; Kirchner, Barbara

    2016-09-01

    Ionic liquids (ILs) have become an established option for the use as electrolytes in dye-sensitized solar cells. In the present study, the adsorption of a multitude of different ILs on a TiO2 surface is studied systematically, focusing on the energetic modifications of the semiconductor. The cation was found to generally cause an energetic downward shift of the TiO2 band levels by accepting electron density from the surface, and the anions were observed to function in the opposite direction, raising the energy levels by donating electron density. Both effects counterbalance each other, leaving the desired outcome dependent on the choice of the specific IL, i.e., the choice of the cation/anion combination. The correlation of the band levels with the properties of the IL was successfully achieved. The dipole moment of the adsorbed ionic liquid species showed little to no correlation with the semiconductor energetics, but the charge transfer calculated by radical Voronoi tessellation revealed a high correlation. The current findings contribute to a deeper understanding of the role of the electrolyte in dye-sensitized solar cells, and ILs in general, and help with choosing and tuning of the electrolyte solutions in existing applications. PMID:27510436

  16. 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

  17. Development of an Ionic-Liquid Absorption Heat Pump

    SciTech Connect

    Holcomb, Don

    2011-03-29

    Solar Fueled Products (SFP) is developing an innovative ionic-liquid absorption heat pump (ILAHP). The development of an ILAHP is extremely significant, as it could result in annual savings of more than 190 billion kW h of electrical energy and $19 billion. This absorption cooler uses about 75 percent less electricity than conventional cooling and heating units. The ILAHP also has significant environmental sustainability benefits, due to reduced CO2 emissions. Phase I established the feasibility and showed the economic viability of an ILAHP with these key accomplishments: • Used the breakthrough capabilities provided by ionic liquids which overcome the key difficulties of the common absorption coolers. • Showed that the theoretical thermodynamic performance of an ILAHP is similar to existing absorption-cooling systems. • Established that the half-effect absorption cycle reduces the peak generator temperature, improving collector efficiency and reducing collector area. • Component testing demonstrated that the most critical components, absorber and generator, operate well with conventional heat exchangers. • Showed the economic viability of an ILAHP. The significant energy savings, sustainability benefits, and economic viability are compelling reasons to continue the ILAHP development.

  18. Antitumor Activity of Ionic Liquids Based on Ampicillin.

    PubMed

    Ferraz, Ricardo; Costa-Rodrigues, João; Fernandes, Maria H; Santos, Miguel M; Marrucho, Isabel M; Rebelo, Luís Paulo N; Prudêncio, Cristina; Noronha, João Paulo; Petrovski, Željko; Branco, Luís C

    2015-09-01

    Significant antiproliferative effects against various tumor cell lines were observed with novel ampicillin salts as ionic liquids. The combination of anionic ampicillin with appropriate ammonium, imidazolium, phosphonium, and pyridinium cations yielded active pharmaceutical ingredient ionic liquids (API-ILs) that show potent antiproliferative activities against five different human cancer cell lines: T47D (breast), PC3 (prostate), HepG2 (liver), MG63 (osteosarcoma), and RKO (colon). Some API-ILs showed IC50 values between 5 and 42 nM, activities that stand in dramatic contrast to the negligible cytotoxic activity level shown by the ampicillin sodium salt. Moreover, very low cytotoxicity against two primary cell lines-skin (SF) and gingival fibroblasts (GF)-indicates that the majority of these API-ILs are nontoxic to normal human cell lines. The most promising combination of antitumor activity and low toxicity toward healthy cells was observed for the 1-hydroxyethyl-3-methylimidazolium-ampicillin pair ([C2 OHMIM][Amp]), making this the most suitable lead API-IL for future studies. PMID:26190053

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

    PubMed

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

    2016-06-14

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

  20. Interactions of Ionic Liquids with Uranium and its Bioreduction

    SciTech Connect

    Zhang, C.; Francis, A.

    2012-09-18

    We investigated the influence of ionic liquids (ILs) 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM]{sup +}[PF{sub 6}]{sup -}, N-ethylpyridinium trifluoroacetate [EtPy]{sup +}[CF{sub 3}COO]{sup -} and N-ethylpyridinium tetrafluoroborate [Et-Py]{sup +}[BF{sub 4}]{sup -} on uranium reduction by Clostridium sp. under anaerobic conditions. Potentiometric titration, UV-vis spectrophotometry, LC-MS and EXAFS analyses showed monodentate complexation between uranyl and BF{sub 4}{sup -} PF{sub 6}{sup -}; and bidentate complexation with CF{sub 3}COO{sup -}. Ionic liquids affected the growth of Clostridium sp. as evidenced by decrease in optical density, changes in pH, gas production, and the extent of U(VI) reduction and precipitation of U(IV) from solution. Reduction of U(VI) to U(IV) was observed in the presence of [EtPy][BF{sub 4}] and [BMIM][PF{sub 6}] but not with [EtPy][CF{sub 3}COO].

  1. Weighing the surface charge of an ionic liquid.

    PubMed

    Hjalmarsson, Nicklas; Wallinder, Daniel; Glavatskih, Sergei; Atkin, Rob; Aastrup, Teodor; Rutland, Mark W

    2015-10-14

    Electrochemical quartz crystal microbalance has been used to measure changes in the composition of the capacitive electrical double layer for 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate, an ionic liquid, in contact with a gold electrode surface as a function of potential. The mass difference between the cation and anion means that the technique can effectively "weigh" the surface charge accurately with high temporal resolution. This reveals quantitatively how changing the potential alters the ratio of cations and anions associated with the electrode surface, and thus the charge per unit area, as well as the kinetics associated with these interfacial processes. The measurements reveal that it is diffusion of co-ions into the interfacial region rather than expulsion of counterions that controls the relaxation. The measured potential dependent double layer capacitance experimentally validates recent theoretical predictions for counterion overscreening (low potentials) and crowding (high potentials) at electrode surfaces. This new capacity to quantitatively measure ion composition is critical for ionic liquid applications ranging from batteries, capacitors and electrodeposition through to boundary layer structure in tribology, and more broadly provides new insight into interfacial processes in concentrated electrolyte solutions. PMID:26370450

  2. (Eco)toxicity and biodegradability of protic ionic liquids.

    PubMed

    Oliveira, Maria V S; Vidal, Bruna T; Melo, Claudia M; de Miranda, Rita de C M; Soares, Cleide M F; Coutinho, João A P; Ventura, Sónia P M; Mattedi, Silvana; Lima, Álvaro S

    2016-03-01

    Ionic liquids (ILs) are often claimed to be "environmentally friendly" compounds however, the knowledge of their potential toxicity towards different organisms and trophic levels is still limited, in particular when protic ionic liquids (PILs) are addressed. This study aims to evaluate the toxicity against various microorganisms and the biodegradability of four PILs namely, N-methyl-2-hydroxyethylammonium acetate, m-2-HEAA; N-methyl-2-hydroxyethylammonium propionate, m-2-HEAPr; N-methyl-2-hydroxyethylammonium butyrate, m-2-HEAB; and N-methyl-2-hydroxyethylammonium pentanoate, m-2-HEAP. The antimicrobial activity was determined against the two bacteria, Sthaplylococcus aureus ATCC-6533 and Escherichia coli CCT-0355; the yeast Candida albicans ATCC-76645; and the fungi Fusarium sp. LM03. The toxicity of all PILs was tested against the aquatic luminescent marine bacterium Vibrio fischeri using the Microtox(®) test. The impact of the PILs was also studied regarding their effect on lettuce seeds (Lactuta sativa). The biodegradability of these PILs was evaluated using the ratio between the biochemical oxygen demand (BOD) and the chemical oxygen demand (COD). The results show that, in general, the elongation of the alkyl chain tends to increase the negative impact of the PILs towards the organisms and biological systems under study. According to these results, m-2-HEAA and m-2-HEAP are the less and most toxic PILs studied in this work, respectively. Additionally, all the PILs have demonstrated low biodegradability. PMID:26796340

  3. Amphiphilic behavior of two phosphonium based ionic liquids.

    PubMed

    Mukherjee, Indrajyoti; Mukherjee, Suvasree; Naskar, Bappaditya; Ghosh, Soumen; Moulik, Satya P

    2013-04-01

    Solution and surface chemical behavior of two phosphonium based ionic liquids triisobutyl (methyl) phosphonium tosylate (IL-1) and trihexyl (tetradecyl) phosphonium bis 2,4,4-(trimethylpentyl)phosphinate (IL-2) have been studied. The polar IL-1 is surface active and water soluble, whereas the weakly polar IL-2 is more surface active with very low aqueous solubility. IL-1 does not form micelles but affects the micellization properties of ionic, nonionic, and zwitterionic surfactants more strongly than conventional electrolytes. IL-2 itself forms micelles and mixed micelles with Triton X-100 (TX-100) in aqueous solution. It also forms Langmuir monolayers of liquid expanded type, at the air/water interface. IL-1 can replace water in forming microemulsions with the oil isopropylmyristate (IPM), stabilized by IL-2 (surfactant)+isopropanol (IP as a co-surfactant) like the IL-1/IPM/(IL-2+IP) system. It produces a large monophasic zone in the pseudoternary phase diagram. The thermodynamics of formation of the microemulsions of IL-1 in oil (IPM) have been examined. The dimensions and the polydispersity of the dispersed nano-droplets in the microemulsions have been determined by DLS. The thermal stability of the microemulsion forming systems has also been studied. ILs studied against Sarcoma-180 cell lines have evidenced proficient anti-cancer activity of IL-1 and moderate activity of IL-2. PMID:23317771

  4. Ionic liquids adsorbed cellulose electro active paper actuator

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

  5. Separation of Fission Products Based on Ionic Liquids: Anion Effect

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V.

    2004-03-28

    The applications of ionic liquids (ILs) as new separation media have been actively investigated recently. The most commonly studied class of ILs for such applications is based on dialkyl imidazolium cations. In comparison with conventional molecular solvents, ILs exhibit enhanced distribution coefficients for a number of complexing neutral ligands in extraction of metal ions from aqueous solutions. The effect of the alkyl chain length of imidazolium cations on the distribution coefficients of solvent extraction using crown ethers was the subject of a number of the previous investigations. The distribution coefficients have been found to decrease with the alkyl chain length of the IL cations. This observation implies that the extraction process also involves the exchange of the IL cations with metal ions. The longer the alkyl chain lengths of the IL cations are, the more hydrophobic the IL cations are and the more difficult to be transported into aqueous phases via ion exchange. Accordingly, the ion-exchange process is another unique property of IL-based extractions involving charged species. Here, we report the investigation about the effect of the variation of IL anions on the solvent extraction of metal ions using crown ethers as extractants. The elucidation of different solvation effects involved in ionic liquids could lead to optimized separation media for these novel solvents.

  6. Photoresponsive Self-Assembly of Surface Active Ionic Liquid.

    PubMed

    Wu, Aoli; Lu, Fei; Sun, Panpan; Gao, Xinpei; Shi, Lijuan; Zheng, Liqiang

    2016-08-16

    A novel photoresponsive surface active ionic liquid (SAIL) 1-(4-methyl azobenzene)-3-tetradecylimidazolium bromide ([C14mimAzo]Br) with azobenzene located in the headgroup was designed. Reversible vesicle formation and rupture can be finely controlled by photostimuli without any additives in the aqueous solution of the single-tailed ionic liquid. The photoisomerization of the azobenzene derivative was investigated by (1)H NMR and UV-vis spectroscopy. Density functional theory (DFT) calculations further demonstrate that trans-[C14mimAzo]Br has less negative interaction energy, which is beneficial to aggregate formation in water. The incorporation of trans-azobenzene group increases the hydrophobicity of the headgroup and reduces the electrostatic repulsion by delocalization of charge, which are beneficial to the formation of vesicles. However, the bend of cis-azobenzene makes the cis-isomers have no ability to accumulate tightly, which induces the rupture of vesicles. Our work paves a convenient way to achieve controlled topologies and self-assembly of single SAIL. PMID:27445115

  7. Ionic liquid biodegradability depends on specific wastewater microbial consortia.

    PubMed

    Docherty, Kathryn M; Aiello, Steven W; Buehler, Barbara K; Jones, Stuart E; Szymczyna, Blair R; Walker, Katherine A

    2015-10-01

    Complete biodegradation of a newly-synthesized chemical in a wastewater treatment plant (WWTP) eliminates the potential for novel environmental pollutants. However, differences within- and between-WWTP microbial communities may alter expectations for biodegradation. WWTP communities can also serve as a source of unique consortia that, when enriched, can metabolize chemicals that tend to resist degradation, but are otherwise promising green alternatives. We tested the biodegradability of three ionic liquids (ILs): 1-octyl-3-methylpyridinium bromide (OMP), 1-butyl-3-methylpyridinium bromide (BMP) and 1-butyl-3-methylimidazolium chloride (BMIM). We performed tests using communities from two WWTPs at three time points. Site-specific and temporal variation both influenced community composition, which impacted the success of OMP biodegradability. Neither BMP nor BMIM degraded in any test, suggesting that these ILs are unlikely to be removed by traditional treatment. Following standard biodegradation assays, we enriched for three consortia that were capable of quickly degrading OMP, BMP and BMIM. Our results indicate WWTPs are not functionally redundant with regard to biodegradation of specific ionic liquids. However, consortia can be enriched to degrade chemicals that fail biodegradability assays. This information can be used to prepare pre-treatment procedures and prevent environmental release of novel pollutants. PMID:25985304

  8. Transformation of acidic poorly water soluble drugs into ionic liquids.

    PubMed

    Balk, Anja; Wiest, Johannes; Widmer, Toni; Galli, Bruno; Holzgrabe, Ulrike; Meinel, Lorenz

    2015-08-01

    Poor water solubility of active pharmaceutical ingredients (API) is a major challenge in drug development impairing bioavailability and therapeutic benefit. This study is addressing the possibility to tailor pharmaceutical and physical properties of APIs by transforming these into tetrabutylphosphonium (TBP) salts, including the generation of ionic liquids (IL). Therefore, poorly water soluble acidic APIs (Diclofenac, Ibuprofen, Ketoprofen, Naproxen, Sulfadiazine, Sulfamethoxazole, and Tolbutamide) were converted into TBP ILs or low melting salts and compared to the corresponding sodium salts. Free acids and TBP salts were characterized by NMR and IR spectroscopy, DSC and XRPD, DVS and dissolution rate measurements, release profiles, and saturation concentration measurements. TBP salts had lower melting points and glass transition temperatures and dissolution rates were improved up to a factor of 1000 as compared to the corresponding free acid. An increase in dissolution rates was at the expense of increased hygroscopicity. In conclusion, the creation of TBP ionic liquids or solid salts from APIs is a valuable concept addressing dissolution and solubility challenges of poorly water soluble acidic compounds. The data suggested that tailor-made counterions may substantially expand the formulation scientist's armamentarium to meet challenges of poorly water soluble drugs. PMID:25976317

  9. Using Ionic Liquids in Selective Hydrocarbon Conversion Processes

    SciTech Connect

    Tang, Yongchun; Periana, Roy; Chen, Weiqun; van Duin, Adri; Nielsen, Robert; Shuler, Patrick; Ma, Qisheng; Blanco, Mario; Li, Zaiwei; Oxgaard, Jonas; Cheng, Jihong; Cheung, Sam; Pudar, Sanja

    2009-09-28

    This is the Final Report of the five-year project Using Ionic Liquids in Selective Hydrocarbon Conversion Processes (DE-FC36-04GO14276, July 1, 2004- June 30, 2009), in which we present our major accomplishments with detailed descriptions of our experimental and theoretical efforts. Upon the successful conduction of this project, we have followed our proposed breakdown work structure completing most of the technical tasks. Finally, we have developed and demonstrated several optimized homogenously catalytic methane conversion systems involving applications of novel ionic liquids, which present much more superior performance than the Catalytica system (the best-to-date system) in terms of three times higher reaction rates and longer catalysts lifetime and much stronger resistance to water deactivation. We have developed in-depth mechanistic understandings on the complicated chemistry involved in homogenously catalytic methane oxidation as well as developed the unique yet effective experimental protocols (reactors, analytical tools and screening methodologies) for achieving a highly efficient yet economically feasible and environmentally friendly catalytic methane conversion system. The most important findings have been published, patented as well as reported to DOE in this Final Report and our 20 Quarterly Reports.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  11. Polarizability effects on the structure and dynamics of ionic liquids

    SciTech Connect

    Cavalcante, Ary de Oliveira; Ribeiro, Mauro C. C.; Skaf, Munir S.

    2014-04-14

    Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibrium structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.

  12. Poly(ionic liquid)/Ionic Liquid Ion-Gels with High "Free" Ionic Liquid Content: Platform Membrane Materials for CO2/Light Gas Separations.

    PubMed

    Cowan, Matthew G; Gin, Douglas L; Noble, Richard D

    2016-04-19

    -films (ca. 100-nm-thick active layer). Traditional polymeric membrane materials are limited by a trade-off between permeability and selectivity empirically described by the "Robeson upper bound"-placing the desired membrane properties beyond reach. Therefore, the investigation of advanced and composite materials that can overcome the limitations of traditional polymeric materials is the focus of significant academic and industrial research. In particular, there has been substantial work on ionic-liquid (IL)-based materials due to their gas transport properties. This review provides an overview of our collaborative work on developing poly(ionic liquid)/ionic liquid (PIL/IL) ion-gel membrane technology. We detail developmental work on the preparation of PIL/IL composites and describe how this chemical technology was adapted to allow the roll-to-roll processing and preparation of membranes with defect-free active layers ca. 100 nm thick, CO2 permeances of over 6000 GPU, and CO2/N2 selectivity of ≥20-properties with the potential to reduce the cost of CO2 removal from coal-fired power plant flue gas to ca. $15 per ton of CO2 captured. Additionally, we examine the materials developments that have produced advanced PIL/IL composite membranes. These advancements include cross-linked PIL/IL blends, step-growth PIL/IL networks with facilitated transport groups, and PIL/IL composites with microporous additives for CO2/CH4 separations. PMID:27046045

  13. Determination of optimal ionic liquid for organic single-crystal field-effect transistors

    NASA Astrophysics Data System (ADS)

    Ono, S.; Miwa, K.; Seki, S.

    2016-02-01

    We investigate organic single-crystal field-effect transistors with various ionic liquids as gate dielectric. We find that the mobility of the field-effect transistors for both p-type and n-type organic semiconductors increases with decreasing total capacitance of the ionic liquid. However, it does not depend on the ion species at the interface between the organic semiconductor and the ionic liquid. By choosing an appropriate ionic liquid, a high carrier mobility of 12.4 cm2/V s in rubrene single crystals (p-type) and 0.13 cm2/V s in 7.7.8.8-Tetracyanoquinodimethane single crystals (n-type) are achieved. This study clarifies the influence of ionic liquids on the device performance of organic field-effect transistors and shows a way to maximize carrier mobility at the solid/liquid interface.

  14. Investigation of Carbon-2 Substituted Imidazoles and Their Corresponding Ionic Liquids

    SciTech Connect

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

    2011-01-01

    The functionality at the C-2 position of the imidazole ring plays a key role in defining the chemical properties of the imidazoles and their corresponding ionic liquids. Imidazoles 1 6 with different C-2 functionality were synthesized and their corresponding ionic liquids were systematically investigated. Based on their physical properties the six imidazoles can be divided into three groups. 1) The imidazoles 2 and 3 are capable of self-polymerization to form poly(ionic liquid)s, and they are characterized with a strong leaving group at the C-2 position. 2) The imidazoles 4 and 5 can form ionic liquids, but they are very sensitive to moisture. 3) The imidazoles 1 and 6 can form stable ionic liquids, and their stabilities were influenced by the electronic effects of the substituents at the C-2 position.

  15. Ionic liquid-modified materials for solid-phase extraction and separation: a review.

    PubMed

    Vidal, Lorena; Riekkola, Marja-Liisa; Canals, Antonio

    2012-02-17

    In recent years, materials science has propelled to the research forefront. Ionic liquids with unique and fascinating properties have also left their footprints to the developments of materials science during the last years. In this review we highlight some of their recent advances and provide an overview at the current status of ionic liquid-modified materials applied in solid-phase extraction, liquid and gas chromatography and capillary electrochromatography with reference to recent applications. In addition, the potential of ionic liquids in the modification of capillary inner wall in capillary electrophoresis is demonstrated. The main target material modified with ionic liquids is silica, but polymers and monoliths have recently joined the studies. Although imidazolium is still clearly the most commonly used ionic liquid for the covalently modification of materials, the exploitation of pyridinium and phosphonium will most probably increase in the future. PMID:22244164

  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. 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

  18. Ionic liquid mixtures--an analysis of their mutual miscibility.

    PubMed

    Omar, Salama; Lemus, Jesus; Ruiz, Elia; Ferro, Víctor R; Ortega, Juan; Palomar, Jose

    2014-03-01

    The use of ionic liquid mixtures (IL-IL mixtures) is being investigated for fine solvent properties tuning of the IL-based systems. The scarce available studies, however, evidence a wide variety of mixing behaviors (from almost ideal to strongly nonideal), depending on both the structure of the IL components and the property considered. In fact, the adequate selection of the cations and anions involved in IL-IL mixtures may ensure the absence or presence of two immiscible liquid phases. In this work, a systematic computational study of the mixing behavior of IL-IL systems is developed by means of COSMO-RS methodology. Liquid-liquid equilibrium (LLE) and excess enthalpy (H(E)) data of more than 200 binary IL-IL mixtures (including imidazolium-, pyridinium-, pyrrolidinium-, ammonium-, and phosphonium-based ILs) are calculated at different temperatures, comparing to literature data when available. The role of the interactions between unlike cations and anions on the mutual miscibility/immiscibility of IL-IL mixtures was analyzed. On the basis of proposed guidelines, a new class of immiscible IL-IL mixtures was reported, which only is formed by imidazolium-based compounds. PMID:24521179

  19. Solid-liquid interfaces of ionic liquid solutions—Interfacial layering and bulk correlations

    NASA Astrophysics Data System (ADS)

    Mezger, Markus; Roth, Roland; Schröder, Heiko; Reichert, Peter; Pontoni, Diego; Reichert, Harald

    2015-04-01

    The influence of the polar, aprotic solvent propylene carbonate on the interfacial structure of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate on sapphire was investigated by high-energy x-ray reflectivity. Experiments at solvent concentrations between 17 mol. % and 83 mol. % bridge the gap between diluted electrolytes described by the classical Gouy-Chapman theory and pure ionic liquids. Analysis of our experimental data revealed interfacial profiles comprised of alternating anion and cation enriched regions decaying gradually into the bulk liquid. With increasing solvent concentration, we observed a decrease in correlation length of the interfacial layering structure. At high ion concentrations, solvent molecules were found to accumulate laterally within the layers. By separating like-charged ions, they reduce their Coulomb repulsion. The results are compared with the bulk structure of IL/solvent blends probed by x-ray scattering and predictions from fundamental fluid theory.

  20. Superfluorinated Ionic Liquid Crystals Based on Supramolecular, Halogen-Bonded Anions.

    PubMed

    Cavallo, Gabriella; Terraneo, Giancarlo; Monfredini, Alessandro; Saccone, Marco; Priimagi, Arri; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Bruce, Duncan W

    2016-05-17

    Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen-bonded supramolecular anions [Cn F2 n+1 -I⋅⋅⋅I⋅⋅⋅I-Cn F2 n+1 ](-) are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen-bonded liquid crystals, and 2) imidazolium-based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation. PMID:27073033

  1. Cold crystallisation behaviour of water molecules in ionic liquids as a screening method to evaluate biocompatibility of the hydrated ionic liquids.

    PubMed

    Fujita, Kyoko; Nikawa, Yohsuke; Ohno, Hiroyuki

    2013-04-21

    Hydrated ionic liquids, exhibiting cold crystallisation behaviour of water molecules in a certain range of water contents, successfully dissolved cytochrome c maintaining the original spin state of heme. PMID:23486783

  2. Porous Membranes Built Up from Hydrophilic Poly(ionic liquid)s.

    PubMed

    Täuber, Karoline; Zimathies, Annett; Yuan, Jiayin

    2015-12-01

    Porous polymer membranes made via electrostatic complexation are fabricated from a water-soluble poly(ionic liquid) (PIL) for the first time. The porous structure is formed as a consequence of simultaneous phase separation of the PIL and ionic complexation with an acid, which occurred in a basic solution of a nonsolvent for the PIL. These membranes have a stimuli-responsive porosity, with open and closed pores in isopropanol and in water, respectively. This property is quantitatively demonstrated in filtration experiments, where water is passing much slower through the membranes than isopropanol. PMID:26469279

  3. Lithium ion conductive behavior of TiO2 nanotube/ionic liquid matrices

    PubMed Central

    2014-01-01

    A series of TiO2 nanotube (TNT)/ionic liquid matrices were prepared, and their lithium ion conductive properties were studied. SEM images implied that ionic liquid was dispersed on the whole surface of TNT. Addition of TNT to ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMImTFSA)) resulted in significant increase of ionic conductivity. Furthermore, lithium transference number was also largely enhanced due to the interaction of anion with TNT. Vogel-Fulcher-Tammann parameter showed higher carrier ion number for TNT/BMImTFSA in comparison with BMImTFSA. PMID:25313300

  4. Enhanced electrical transport in ionic liquid dispersed TMAI-PEO solid polymer electrolyte

    SciTech Connect

    Gupta, Neha; Rathore, Munesh Dalvi, Anshuman; Kumar, Anil

    2014-04-24

    A polymer composite is prepared by dispersing ionic liquid [Bmim][BF{sub 4}] in Polyethylene oxide-tetra methyl ammonium iodide composite and subsequent microwave treatment. X-ray diffraction patterns confirm the composite nature. To explore possibility of proton conductivity in these films, electrical transport is studied by impedance spectroscopy and DC polarization. It is revealed that addition of ionic liquid in host TMAI-PEO solid polymer electrolyte enhances the conductivity by ∼ 2 orders of magnitude. Polarization measurements suggest that composites are essentially ion conducting in nature. The maximum ionic conductivity is found to be ∼2 × 10{sup −5} for 10 wt % ionic liquid.

  5. Water-in-ionic liquid microemulsion formation in solvent mixture of aprotic and protic imidazolium-based ionic liquids.

    PubMed

    Kusano, Takumi; Fujii, Kenta; Hashimoto, Kei; Shibayama, Mitsuhiro

    2014-10-14

    We report that water-in-ionic liquid microemulsions (MEs) are stably formed in an organic solvent-free system, i.e., a mixture of aprotic (aIL) and protic (pIL) imidazolium-based ionic liquids (ILs) containing the anionic surfactant dioctyl sulfosuccinate sodium salt (AOT). Structural investigations using dynamic light, small-angle X-ray, and small-angle neutron scatterings were performed for MEs formed in mixtures of aprotic 1-octyl-3-methylimidazolium ([C8mIm(+)]) and protic 1-alkylimidazolium ([CnImH(+)], n = 4 or 8) IL with a common anion, bis(trifluoromethanesulfonyl)amide ([TFSA(-)]). It was found that the ME structure strongly depends on the mixing composition of the aIL/pIL in the medium. The ME size appreciably increases with increasing pIL content in both [C8mIm(+)][TFSA(-)]/[C8ImH(+)][TFSA(-)] and [C8mIm(+)][TFSA(-)]/[C4ImH(+)][TFSA(-)] mixtures. The size is larger for the n = 8 system than that for the n = 4 system. These results indicate that the shell part of MEs is composed of both AOT and pIL cation, and the ME size can be tuned by pIL content in the aIL/pIL mixtures. PMID:25226398

  6. Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

    PubMed

    Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

    2016-02-10

    Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3

  7. Viscosity Measurements on Ionic Liquids: A Cautionary Tale

    NASA Astrophysics Data System (ADS)

    Diogo, João C. F.; Caetano, Fernando J. P.; Fareleira, João M. N. A.; Wakeham, William A.

    2014-10-01

    The vibrating-wire viscometer has proven to be an exceedingly effective means of determining the viscosity of liquids over a wide range of temperature and pressure. The instrument has a long history but a variety of technological and theoretical developments over a number of years have improved its precision and most recently have enabled absolute measurements of high accuracy. However, the nature of the electrical measurements required for the technique has inhibited its widespread use for electrically conducting liquids so that there have been only a limited number of measurements. In the particular context of ionic liquids, which have themselves attracted considerable attention, this is unfortunate because it has meant that one primary measurement technique has seldom been employed for studies of their viscosity. In the last 2 years systematic efforts have been made to explore the applicability of the vibrating-wire technique by examining a number of liquids of increasing electrical conductivity. These extensions have been successful. However, in the process we have had cause to review previous studies of the viscosity and density of the same liquids at moderate temperatures and pressures and significant evidence has been accumulated to cause concern about the application of a range of viscometric techniques to these particular fluids. Because the situation is reminiscent of that encountered for a new set of environmentally friendly refrigerants at the end of the last decade, in this paper the experimental methods employed with these liquids have been reviewed which leads to recommendations for the handling of these materials that may have consequences beyond viscometric measurements. In the process new viscosity and density data for 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [mim][], 1-ethyl-3-methylimidazolium ethyl sulfate [mim][], and 1-ethyl-3-methylpyridinium ethyl sulfate [mpy][] have been obtained.

  8. Low-frequency Raman spectra and fragility of imidazolium ionic liquids

    SciTech Connect

    Ribeiro, Mauro C. C.

    2010-07-14

    Raman spectra within the 5-200 cm{sup -1} range have been recorded as a function of temperature for different ionic liquids based on imidazolium cations. A correlation has been found between fragility and the temperature dependence of the strength of fast relaxational motions. Understanding quasielastic scattering as the relaxational contribution to ionic mean-squared displacement elucidates some effects on ionic liquids' fragility resulting from modifications in the chemical structure.

  9. Bis-sulfonic acid ionic liquids for the conversion of fructose to 5-hydroxymethyl-2-furfural.

    PubMed

    Sim, Sang Eun; Kwon, Sunjeong; Koo, Sangho

    2012-01-01

    Homogenous bis-sulfonic acid ionic liquids (1 mol equiv.) in DMSO (10 mol equiv.) at 100 °C efficiently mediated the conversion of D-fructose into 5-hydroxymethyl-2-furfural in 75% isolated yield, which was roughly a 10% increment compared to the case of the mono-sulfonic acid ionic liquids. PMID:23114616

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

    PubMed

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

    2012-03-20

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

  11. Visualization of Biomass Solubilization and Cellulose Regeneration during Ionic Liquid Pretreatment of Switchgrass

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Auto-fluorescent mapping of plant cell walls was used to visualize cellulose and lignin in pristine switchgrass (Panicum virgatum) stems to determine the mechanisms of biomass dissolution during ionic liquid pretreatment. The addition of ground switchgrass to the ionic liquid 1-n-ethyl-3-methylimid...

  12. Thermochromism and switchable paramagnetism of cobalt(II) in thiocyanate ionic liquids.

    PubMed

    Osborne, Stephen J; Wellens, Sil; Ward, Chris; Felton, Solveig; Bowman, Robert M; Binnemans, Koen; Swadźba-Kwaśny, Małgorzata; Gunaratne, H Q Nimal; Nockemann, Peter

    2015-07-01

    Temperature-dependent switching of paramagnetism of a cobalt(II) complex is observed in an ionic liquid solution. Paramagnetic and thermochromic switching occur simultaneously due to a reversible change in coordination. This reversible switching is possible in the ionic liquid solution, which enables mobility of thiocyanate anions by remaining mobile at low temperatures and acts as an anion reservoir. PMID:26053484

  13. Concentration-dependent apparent partition coefficients of ionic liquids possessing ethyl- and bi-sulphate anions.

    PubMed

    Jain, Preeti; Kumar, Anil

    2016-01-14

    This study deals with the concentration dependent apparent partition coefficients log P of the ethyl and bisulfate-based ionic liquids. It is observed that the bisulfate-based ionic liquids show different behaviour with respect to concentration as compared to ethyl sulphate-based ionic liquids. It is significant and useful analysis for the further implementation of alkyl sulfate based ionic liquids as solvents in extraction processes. The log P values of the ethyl sulphate-based ionic liquids were noted to vary linearly with the concentration of the ionic liquid, whereas a flip-flop trend with the concentration for the log P values of the bisulphate-based ionic liquids was observed due to the difference in hydrogen bond accepting basicity and possibility of aggregate formation of these anions. The π-π interactions between the imidazolium and pyridinium rings were seen to affect the log P values. The alkyl chain length of anions was also observed to influence the log P values. The hydrophobicity of ionic liquid changes with the alkyl chain in the anion in the order; [HSO4](-) < [EtSO4](-) < [BuSO4](-). PMID:26660452

  14. Polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials and their chromatographic applications.

    PubMed

    Qiu, Hongdeng; Jiang, Shengxiang; Takafuji, Makoto; Ihara, Hirotaka

    2013-03-25

    New polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials were designed based on the preparation of a new polymerizable azobenzene anionic monomer and either its cation-exchange with alkylimidazolium after grafting or the formation of an ionic liquid monomer pair before grafting onto silica. PMID:23417018

  15. Direct UV-spectroscopic measurement of selected ionic-liquid vapors

    SciTech Connect

    Dai, Sheng; Luo, Huimin; Wang, Congmin; Li, Haoran

    2010-01-01

    The hallmark of ionic liquids lies in their negligible vapor pressure. This ultralow vapor pressure makes it difficult to conduct the direct spectroscopic measurement of ionic-liquid vapors. In fact, there have been no electronic spectroscopic data currently available for ionic-liquid vapors. This deficiency significantly hampers the fundamental understanding of the unique molecular structures of ionic liquids. Herein, the UV absorption spectra of eight ionic liquids, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim{sup +}] [Tf{sub 2}N{sup -}]) and 1-ethyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide ([Emim{sup +}][beti{sup -}]) in the vapor phase in a distillation-like environment, were measured through a high-temperature spectroscopic technique to fill this knowledge gap. Two strong absorption peaks of the [Bmim{sup +}][Tf{sub 2}N{sup -}] vapor lie at 202 and 211 nm, slightly different from those of the neat [Bmim{sup +}][Tf{sub 2}N{sup -}] thin film and its solution in water. Based on the quantitative determination of the vapor absorption spectra as a function of temperature, the vaporization enthalpies of these ionic liquids vapors were measured and found to be in good agreement with the corresponding literature values. This in situ method opens up a new avenue to study the nature of ionic-liquid vapors and to determine the vaporization enthalpies of ionic liquids.

  16. Ionic Liquid as a Solvent and Catalyst for Acylation of Maltodextrin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Catalyst-free esterification of maltodextrin was carried out in ionic liquid. Stearate esters of maltodextrin were obtained in various degree of substitution (DS) when vinyl stearate or stearic acid was heated with maltodextrin in ionic liquid, 1-butyl-3-methylimidazolium cyanamide (bmim[dca]). Re...

  17. Comparison of Three Ionic Liquid-Tolerant Cellulases by Molecular Dynamics

    PubMed Central

    Jaeger, Vance; Burney, Patrick; Pfaendtner, Jim

    2015-01-01

    We have employed molecular dynamics to investigate the differences in ionic liquid tolerance among three distinct family 5 cellulases from Trichoderma viride, Thermogata maritima, and Pyrococcus horikoshii. Simulations of the three cellulases were conducted at a range of temperatures in various binary mixtures of the ionic liquid 1-ethyl-3-methyl-imidazolium acetate with water. Our analysis demonstrates that the effects of ionic liquids on the enzymes vary in each individual case from local structural disturbances to loss of much of one of the enzyme’s secondary structure. Enzymes with more negatively charged surfaces tend to resist destabilization by ionic liquids. Specific and unique structural changes in the enzymes are induced by the presence of ionic liquids. Disruption of the secondary structure, changes in dynamical motion, and local changes in the binding pocket are observed in less tolerant enzymes. Ionic-liquid-induced denaturation of one of the enzymes is indicated over the 500 ns timescale. In contrast, the most tolerant cellulase behaves similarly in water and in ionic-liquid-containing mixtures. Unlike the heuristic approaches that attempt to predict enzyme stability using macroscopic properties, molecular dynamics allows us to predict specific atomic-level structural and dynamical changes in an enzyme’s behavior induced by ionic liquids and other mixed solvents. Using these insights, we propose specific experimentally testable hypotheses regarding the origin of activity loss for each of the systems investigated in this study. PMID:25692593

  18. 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 %.

  19. Synthesis and Characterization of Novel Dimeric Ionic Liquids by Conventional Approaches

    PubMed Central

    Ganesan, Kilivelu; Alias, Yatimah

    2008-01-01

    The 1H-NMR shifts of the imidazolium protons of some novel dimeric ionic liquids were examined in various deuterated solvents. Interactions between the solvent and the imidazolium salt of butyl substituted ionic liquids were observed to give higher chemical shifts than methyl substitution. PMID:19325800

  20. Exploiting hydrophobic borohydride-rich ionic liquids as faster-igniting rocket fuels.

    PubMed

    Liu, Tianlin; Qi, Xiujuan; Huang, Shi; Jiang, Linhai; Li, Jianling; Tang, Chenglong; Zhang, Qinghua

    2016-02-01

    A family of hydrophobic borohydride-rich ionic liquids was developed, which exhibited the shortest ignition delay times of 1.7 milliseconds and the lowest viscosity (10 mPa s) of hypergolic ionic fluids, demonstrating their great potential as faster-igniting rocket fuels to replace toxic hydrazine derivatives in liquid bipropellant formulations. PMID:26687630