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Sample records for aprotic ionic liquids

  1. Interactions in ion pairs of protic ionic liquids: Comparison with aprotic ionic liquids

    NASA Astrophysics Data System (ADS)

    Tsuzuki, Seiji; Shinoda, Wataru; Miran, Md. Shah; Kinoshita, Hiroshi; Yasuda, Tomohiro; Watanabe, Masayoshi

    2013-11-01

    The stabilization energies for the formation (Eform) of 11 ion pairs of protic and aprotic ionic liquids were studied by MP2/6-311G** 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 Eform for the [dema][CF3SO3] and [dmpa][CF3SO3] complexes (-95.6 and -96.4 kcal/mol, respectively) are significantly larger (more negative) than that for the [etma][CF3SO3] complex (-81.0 kcal/mol). The same trend was observed for the calculations of ion pairs of the three cations with the Cl-, BF4-, TFSA- anions. The anion has contact with the N-H bond of the dema+ or dmpa+ cations in the most stable geometries of the dema+ and dmpa+ 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 Eform for the less stable geometries for the dema+ and dmpa+ complexes are close to those for the most stable etma+ 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- anion, while the strong directionality of the interactions was not suggested from the simulation of the [etma][CF3SO3] ionic liquid.

  2. Interactions in ion pairs of protic ionic liquids: comparison with aprotic ionic liquids.

    PubMed

    Tsuzuki, Seiji; Shinoda, Wataru; Miran, Md Shah; Kinoshita, Hiroshi; Yasuda, Tomohiro; Watanabe, Masayoshi

    2013-11-01

    The stabilization energies for the formation (E(form)) of 11 ion pairs of protic and aprotic ionic liquids were studied by MP2/6-311G** 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(form) for the [dema][CF3SO3] and [dmpa][CF3SO3] complexes (-95.6 and -96.4 kcal/mol, respectively) are significantly larger (more negative) than that for the [etma][CF3SO3] complex (-81.0 kcal/mol). The same trend was observed for the calculations of ion pairs of the three cations with the Cl(-), BF4(-), TFSA(-) anions. The anion has contact with the N-H bond of the dema(+) or dmpa(+) cations in the most stable geometries of the dema(+) and dmpa(+) 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(form) for the less stable geometries for the dema(+) and dmpa(+) complexes are close to those for the most stable etma(+) 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(-) anion, while the strong directionality of the interactions was not suggested from the simulation of the [etma][CF3SO3] ionic liquid. PMID:24206313

  3. 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 NH 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 11.018.0 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 NH bonds of the cations have contact with the negatively charged (oxygen and nitrogen) atoms of TFSA{sup ?} anion, while the strong directionality of the interactions was not suggested from the simulation of the [etma][CF{sub 3}SO{sub 3}] ionic liquid.

  4. Ionic liquids and reactive azeotropes: the continuity of the aprotic and protic classes.

    PubMed

    Canongia Lopes, Jos N; Rebelo, Lus Paulo N

    2010-02-28

    In this work, we explore the relations between the acid-base reactions implicit in the definition of protic ionic liquids and their solutions, the existence of reactive azeotropy, and the continuity between the aprotic and protic classes of ionic liquids. The profound impact caused by this type of homogenous azeotropy on the fluid phase behaviour (liquid-gas equilibria) of this class of compounds is also discussed. PMID:20145863

  5. Non-ionogenic amphiphiles in aprotic ionic liquids

    NASA Astrophysics Data System (ADS)

    Zherenkova, L. V.; Komarov, P. V.

    2015-04-01

    Structural properties of the imidazolium ionic liquid-non-ionogenic amphiphile system are studied on the basis of the integral equation theory. The effect of the alkyl substituent lengths of cations and solvent selectivity on the features of amphiphile self-assembly is studied. The need to allow for solvent structure in constructing a theory of phase behavior of amphiphile in ionic liquid is demonstrated. The characteristic scales of structural inhomogeneities of a mixture at the stage of the self-assembly of amphiphile molecules are analyzed. Aggregation characteristics of mixture, particularly medium-field spinodal temperature are calculated, depending on amphiphile concentration.

  6. A comparative study of the terrestrial ecotoxicity of selected protic and aprotic ionic liquids.

    PubMed

    Peric, Brezana; Sierra, Jordi; Mart, Esther; Cruaas, Robert; Garau, Maria Antonia

    2014-08-01

    Ionic liquids (ILs) are a fairly new and very promising group of compounds with a vast variety of possible structures and uses. They are considered to be potentially "green", but their impact on the environment tends to be neglected or not studied enough, especially when it comes to terrestrial ecotoxicity, where there are very few studies performed to date. This work presents a comparative study of the terrestrial ecotoxicity of selected representatives of two ILs groups: a new family of protic ILs (derived from aliphatic amines and organic acids) and some frequently used aprotic ILs (substituted imidazolium and piridinium chlorides). Toxicity of the ILs towards three terrestrial plant species (Allium cepa, Lolium perenne and Raphanus sativus) and soil microorganisms involved in carbon and nitrogen transformation was analyzed. Protic ILs have shown no toxic effect in most of the tests performed. The EC50 values for aprotic ILs are various orders of magnitude lower than the ones for protic ILs in all of the tests. The most toxic ILs are the most complex ones in both of the analyzed groups. Protic ILs seem to have a potential for biodegradation in soil, while aprotic ILs exhibit inhibitory effects towards the carbon transforming microbiota. These findings indicate that protic ILs can be considered as less toxic and safer for the terrestrial environment than the aprotic ILs. PMID:24630250

  7. 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

  8. Physical Absorption Of CO2 in Protic and Aprotic Ionic Liquids: An Interaction Perspective.

    PubMed

    Izgorodina, Ekaterina I; Hodgson, Jennifer L; Weis, Derick C; Pas, Steven J; MacFarlane, Douglas R

    2015-09-01

    The physical absorption of CO2 by protic and aprotic ionic liquids such as 1-ethyl-3-methyl-imidazolium tetrafluoroborate was examined at the molecular level using symmetry adapted perturbation theory (SAPT) and density functional techniques through comparison of interaction energies of noncovalently bound complexes between the CO2 molecule and a series of ionic liquid ions and ion pairs. These energies were contrasted with those for complexes with model amines such as methylamine, dimethylamine, and trimethylamine. Detailed analysis of the five fundamental forces that are responsible for stabilization of the complexes is discussed. It was confirmed that the nature of the anion had a greater effect upon the physical interaction energy in non functionalized ionic liquids, with dispersion forces playing an important role in CO2 solubility. Hydrogen bonding with protic cations was shown to impart additional stability to the noncovalently bound CO2IL complex through inductive forces. Two solvation models, the conductor-like polarizable continuum model (CPCM) and the universal solvation model (SMD), were used to estimate the impact of solvent effects on the CO2 binding. Both solvent models reduced interaction energies for all types of ions. These interaction energies appeared to favor imidazolium cations and carboxylic and sulfonic groups as well as bulky groups (e.g., NTf2) in anions for the physical absorption of CO2. The structure-reactivity relationships determined in this study may help in the optimization of the physical absorption process by means of ionic liquids. PMID:26267781

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

    PubMed Central

    Hollczki, 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 domainspolar and nonpolarthree 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

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

    PubMed

    Hollczki, 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

  11. Elucidating Interactions and Conductivity of Newly Synthesised Low Bandgap Polymer with Protic and Aprotic Ionic Liquids

    PubMed Central

    Attri, Pankaj; Lee, Seung-Hyun; Hwang, Sun Woo; Kim, Joong I. L.; Lee, Sang Woo; Kwon, Gi-Chung; Choi, Eun Ha; Kim, In Tae

    2013-01-01

    In this paper, we have examined the conductivity and interaction studies of ammonium and imidazolium based ionic liquids (ILs) with the newly synthesised low bandgap polymer (Poly(2-heptadecyl-4-vinylthieno[3,4-d]thiazole) (PHVTT)). Use of low bandgap polymers is the most suitable way to harvest a broader spectrum of solar radiations for solar cells. But, still there is lack of most efficient low bandgap polymer. In order to solve this problem, we have synthesised a new low bandgap polymer and investigated its interaction with the ILs to enhance its conductivity. ILs may undergo almost unlimited structural variations; these structural variations have attracted extensive attention in polymer studies. The aim of present work is to illustrate the state of art progress of implementing the interaction of ILs (protic and aprotic ILs) with newly synthesised low bandgap polymer. In addition to this, our UV-Vis spectroscopy, confocal Raman spectroscopy and FT-IR spectroscopy results have revealed that all studied ILs (tributylmethylammonium methyl sulfate ([N1444][MeSO4] from ammonium family) and 1-methylimidazolium chloride ([Mim]Cl, and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl from imidazolium family) have potential to interact with polymer. Our semi empirical calculation with help of Hyperchem 7 shows that protic IL ([Mim]Cl) interacts strongly with the low bandgap polymer through the H-bonding. Further, protic ILs shows enhanced conductivity than aprotic ILs in association with low bandgap polymer. This study provides the combined effect of low bandgap polymer and ILs that may generate many theoretical and experimental opportunities. PMID:23874829

  12. Comparison of aggregation behaviors of a phytosterol ethoxylate surfactant in protic and aprotic ionic liquids.

    PubMed

    Yue, Xiu; Chen, Xiao; Li, Qintang

    2012-08-01

    Two different room-temperature ionic liquids (ILs), the protic ethylammonium nitrate (EAN) and the aprotic 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF(4)), have been employed to investigate the solvent protonation effect on aggregation behaviors of a phytosterol ethoxylate surfactant (BPS-10). The calculated thermodynamic parameters based on surface tension measurements present a stronger solvophobic interaction in EAN than that in [Bmim]BF(4) and disclose different driving forces for micelle formation. In addition, the polarized optical microscopy and small-angle X-ray scattering techniques are used to characterize the phase structures formed in both systems at 25 C. Due to the H-bonding networks in protic EAN, BPS-10 exhibits a lyotropic liquid-crystalline behavior different from that in [Bmim]BF(4). Results obtained from the rheological measurements reflect a more viscoelastic nature of lyotropic liquid-crystalline phases in EAN. The obtained results indicate that the protic EAN behaves more effective than [Bmim]BF(4) to promote the nonionic BPS-10 aggregation. PMID:22793994

  13. Surface interactions, corrosion processes and lubricating performance of protic and aprotic ionic liquids with OFHC copper

    NASA Astrophysics Data System (ADS)

    Espinosa, Tulia; Sanes, Jos; Jimnez, Ana-Eva; Bermdez, Mara-Dolores

    2013-05-01

    In order to select possible candidates for use as lubricants or as precursors of surface coatings, the corrosion and surface interactions of oxygen-free high conductivity (OFHC) copper with two new protic (PIL) and four aprotic (APIL) room-temperature ionic liquids have been studied. The PILs, with no heteroatoms in their composition, are the triprotic di[(2-hydroxyethyl)ammonium] succinate (MSu) and the diprotic di[bis-(2-hydroxyethyl)ammonium] adipate (DAd). The four APILs contain imidazolium cations with short or long alkyl chain substituents and reactive anions: 1-ethyl-3-methylimidazolium phosphonate ([EMIM]EtPO3H); 1-ethyl-3-methylimidazolium octylsulfate ([EMIM]C8H17SO4); 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM]BF4) and 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF6). Contact angles between the ionic liquids and OFHC copper surface were measured. Mass and roughness changes of OFHC copper after 168 h in contact with the ionic liquids have been determined. Copper surfaces were studied by XRD, SEM-EDX and XPS surface analysis. FTIR spectra of the liquid phases recovered after being in contact with the copper surface were compared with that of the neat ionic liquids. The lowest corrosion rate is observed for the diprotic ammonium adipate PIL (DAd), which gives low mass and surface roughness changes and forms adsorbed layers on copper, while the triprotic ammonium succinate salt (MSu) produces a severe corrosive attack by reaction with copper to form a blue crystalline solid, which has been characterized by FTIR and thermal analysis (TGA). All imidazolium APILs react with copper, with different results as a function of the anion. As expected, [EMIM]C8H17SO4 reacts with copper to form the corresponding copper sulphate salt. [EMIM]EtPO3H produces severe corrosion to form a phosphonate-copper soluble phase. [HMIM]BF4 gives rise to the highest roughness increase of the copper surface. [HMIM]PF6 shows the lowest mass and roughness changes of the four imidazolium ionic liquids due to the formation of a solid layer containing phosphorus and fluorine. The results described in the present study are in agreement with the outstanding good tribological performance of the diprotic ammonium adipate (DAd) ionic liquid for the copper-copper contact, in pin-on-disc tests, preventing wear and giving a very low friction coefficient of 0.01. Under the same conditions, [HMIM]PF6 gives a friction value of 0.03, while the reactivity of MSu towards copper produces maximum friction peaks of 0.05. In contrast with the absence of surface damage on copper, an abrasive wear mechanism is observed for MSu and [HMIM]PF6. The results confirm a better lubricating performance for a lower corrosion rate.

  14. 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.

  15. Chemically tunable ionic liquids with aprotic heterocyclic anion (AHA) for CO(2) capture.

    PubMed

    Seo, Samuel; Quiroz-Guzman, Mauricio; DeSilva, M Aruni; Lee, Tae Bum; Huang, Yong; Goodrich, Brett F; Schneider, William F; Brennecke, Joan F

    2014-05-29

    Ionic liquids (ILs) with aprotic heterocyclic anions, or AHAs, can bind CO2 with reaction enthalpies that are suitable for gas separations and without suffering large viscosity increases. In the present work, we have synthesized ILs bearing an alkyl-phosphonium cation with indazolide, imidazolide, pyrrolide, pyrazolide and triazolide-based anions that span a wide range of predicted reaction enthalpies with CO2. Each AHA-based IL was characterized by NMR spectroscopy and their physical properties (viscosity, glass transition, and thermal decomposition temperature) determined. In addition, the influence of substituent groups on the reaction enthalpy was investigated by measuring the CO2 solubility in each IL at pressures between 0 and 1 bar at 22 °C using a volumetric method. The isotherm-derived enthalpies range between -37 and -54 kJ mol(-1) of CO2, and these values are in good agreement with computed enthalpies of gas-phase IL-CO2 reaction products from molecular electronic structure calculations. The AHA ILs show no substantial increase in viscosity when fully saturated with CO2 at 1 bar. Phase splitting and compositional analysis of one of the IL/H2O and IL/H2O/CO2 systems conclude that protonation of the 2-cyanopyrrolide anion is improbable, and this result was confirmed by the equimolar CO2 absorption in the presence of water. Taking advantage of the tunable binding energy and absence of viscosity increase after the reaction with CO2, AHA ILs are promising candidates for efficient and environmental-friendly absorbents in postcombustion CO2 capture. PMID:24811264

  16. Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions

    SciTech Connect

    Seo, S; DeSilva, MA; Brennecke, JF

    2014-12-25

    Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim](+)) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange process between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using H-1 and C-13 NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 degrees C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.

  17. Gelation mechanism of tetra-armed poly(ethylene glycol) in aprotic ionic liquid containing nonvolatile proton source, protic ionic liquid.

    PubMed

    Hashimoto, Kei; Fujii, Kenta; Nishi, Kengo; Sakai, Takamasa; Yoshimoto, Nobuko; Morita, Masayuki; Shibayama, Mitsuhiro

    2015-04-01

    We report the gelation mechanism of tetra-armed prepolymer chains in typical aprotic ionic liquid (aIL), i.e., A-B type cross-end coupling reaction of tetra-armed poly(ethylene glycol)s with amine and activated ester terminals (TetraPEG-NH2 and TetraPEG-NHS, respectively) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mIm][TFSA]). In the ion gel system, we focused on the pH (or H(+) concentration) dependence of the gelation reaction. We thus applied the protic ionic liquid (pIL), 1-ethylimidazolium TFSA ([C2ImH][TFSA]), as a nonvolatile H(+) source, and added it into the solvent aIL. It was found that the gelation time of TetraPEG ion gel can be successfully controlled from 1 min to 3 h depending on the concentration of pIL (cpIL = 0-3 mM). This suggests that the acid-base properties of TetraPEG-NH2 showing acid-base equilibrium (-NH2 + H(+) ? -NH3(+)) in the solutions play a key role in the gelation process. The acid dissociation constants, pKa's of TetraPEG-NH3(+) and C2ImH(+) (cation of pIL) in aIL were directly determined by potentiometric titration to be 16.4 and 13.7, respectively. This indicates that most of the H(+) ions bind to TetraPEG-NH2 and then C2ImH(+) exists as neutral C2Im. The reaction efficiency of amide bond (cross-linked point) systematically decreased with increasing cpIL, which was reflected to the mechanical strength of the ion gels. From these results, we discuss the gelation mechanism of TetraPEG in aIL to point out the relationship between polymer network structure and [H(+)] in the solutions. PMID:25768427

  18. Study of a Li-air battery having an electrolyte solution formed by a mixture of an ether-based aprotic solvent and an ionic liquid

    NASA Astrophysics Data System (ADS)

    Cecchetto, Laura; Salomon, Mark; Scrosati, Bruno; Croce, Fausto

    2012-09-01

    Recent studies have clearly demonstrated that cyclic and linear carbonates are unstable when used in rechargeable Li-air batteries employing aprotic solvents mostly due to the cathodic formation of superoxide during the oxygen reduction reaction. In particular, it has been ascertained that nucleophilic attack by superoxide anion radical, O2-rad , at O-alkyl carbon is a common mechanism of decomposition of organic carbonates. Moreover, theoretical calculations showed that ether chemical functionalities are stable against nucleophilic substitution induced by superoxide. Aim of this study is to report on a new electrolyte solution for Li-air battery formed by a mixture of an ether-based aprotic solvent with an ionic liquid (IL). The IL-based electrolyte was obtained by mixing the pure ionic liquid N-methyl-(n-butyl) pyrrolidinium bis(trifluoromethane sulfonyl) imide (here denoted as PYR14TFSI) to a 0.91 M solution of lithium triflate (LiCF3SO3) in tetra ethylene glycol dimethyl etcher (TEGDME). We observed that the presence of IL beneficially affects the kinetics and the reversibility of the oxygen reactions involved at the cathode. The most significant result being a lower overvoltage for the charge reaction, compared to a Li/air cell containing the same electrolyte solution without IL.

  19. A wave-function based approach for polarizable charge model: Systematic comparison of polarization effects on protic, aprotic, and ionic liquids

    NASA Astrophysics Data System (ADS)

    Nakano, Hiroshi; Yamamoto, Takeshi; Kato, Shigeki

    2010-01-01

    We first describe a wave-function based formalism of polarizable charge model by starting from the Hartree product ansatz for the total wave function and making the second-order expansion of individual molecular energies with the use of partial charge operators. The resulting model is shown to be formally equivalent to the charge response kernel model that starts from the linear-response approximation to partial charges, and also closely related to a family of fluctuating charge models that are based on the electronegativity equalization principle. We then apply the above model to a systematic comparison of polarization effects on qualitatively different liquids, namely, protic solvents (water and methanol), an aprotic polar solvent (acetonitrile), and imidazolium-based ionic liquids. Electronic polarization is known to decelerate molecular motions in conventional solvents while it accelerates them in ionic liquids. To obtain more insights into these phenomena, we consider an effective decomposition of total polarization energy into molecular contributions, and show that their statistical distribution is well-correlated with the acceleration/deceleration of molecular motions. In addition, we perform effective nonpolarizable simulations based on mean polarized charges, and compare them with fully polarizable simulations. The result shows that the former can reproduce structural properties of conventional solvents rather accurately, while they fail qualitatively to reproduce acceleration of molecular motions in ionic liquids.

  20. Are alkyl sulfate-based protic and aprotic ionic liquids stable with water and alcohols? A thermodynamic approach.

    PubMed

    Jacquemin, Johan; Goodrich, Peter; Jiang, Wei; Rooney, David W; Hardacre, Christopher

    2013-02-14

    The knowledge of the chemical stability as a function of the temperature of ionic liquids (ILs) in the presence of other molecules such as water is crucial prior to developing any industrial application and process involving these novel materials. Fluid phase equilibria and density over a large range of temperature and composition can give basic information on IL purity and chemical stability. The IL scientific community requires accurate measurements accessed from reference data. In this work, the stability of different alkyl sulfate-based ILs in the presence of water and various alcohols (methanol, ethanol, 1-butanol, and 1-octanol) was investigated to understand their stability as a function of temperature up to 423.15 K over the hydrolysis and transesterification reactions, respectively. From this investigation, it was clear that methyl sulfate- and ethyl sulfate-based ILs are not stable in the presence of water, since hydrolysis of the methyl sulfate or ethyl sulfate anions to methanol or ethanol and hydrogenate anion is undoubtedly observed. Such observations could help to explain the differences observed for the physical properties published in the literature by various groups. Furthermore, it appears that a thermodynamic equilibrium process drives these hydrolysis reactions. In other words, these hydrolysis reactions are in fact reversible, providing the possibility to re-form the desired alkyl sulfate anions by a simple transesterification reaction between hydrogen sulfate-based ILs and the corresponding alcohol (methanol or ethanol). Additionally, butyl sulfate- and octyl sulfate-based ILs appear to follow this pattern but under more drastic conditions. In these systems, hydrolysis is observed in both cases after several months for temperatures up to 423 K in the presence of water. Therein, the partial miscibility of hydrogen sulfate-based ILs with long chain alcohols (1-butanol and 1-octanol) can help to explain the enhanced hydrolytic stability of the butyl sulfate- and octyl sulfate-based ILs compared with the methyl or ethyl sulfate systems. Additionally, rapid transesterification reactions are observed during liquid-liquid equilibrium studies as a function of temperature for binary systems of (hydrogen sulfate-based ionic liquids + 1-butanol) and of (hydrogen sulfate-based ionic liquids + 1-octanol). Finally, this atom-efficient catalyst-free transesterification reaction between hydrogen sulfate-based ILs and alcohol was then tested to provide a novel way to synthesize new ILs with various anion structures containing the alkyl sulfate group. PMID:23320846

  1. Ionic Grease Lubricants: Protic [Triethanolamine][Oleic Acid] and Aprotic [Choline][Oleic Acid].

    PubMed

    Mu, Liwen; Shi, Yijun; Ji, Tuo; Chen, Long; Yuan, Ruixia; Wang, Huaiyuan; Zhu, Jiahua

    2016-02-24

    Ionic liquid lubricants or lubricant additives have been studied intensively over past decades. However, ionic grease serving as lubricant has rarely been investigated so far. In this work, novel protic [triethanolamine][oleic acid] and aprotic [choline][oleic acid] ionic greases are successfully synthesized. These ionic greases can be directly used as lubricants without adding thickeners or other additives. Their distinct thermal and rheological properties are investigated and are well-correlated to their tribological properties. It is revealed that aprotic ionic grease shows superior temperature- and pressure-tolerant lubrication properties over those of protic ionic grease. The lubrication mechanism is studied, and it reveals that strong physical adsorption of ionic grease onto friction surface plays a dominating role for promoted lubrication instead of tribo-chemical film formation. PMID:26815603

  2. Application of room-temperature aprotic and protic ionic liquids for oxidative folding of cysteine-rich peptides.

    PubMed

    Heimer, Pascal; Tietze, Alesia A; Bhm, Miriam; Giernoth, Ralf; Kuchenbuch, Andrea; Stark, Annegret; Leipold, Enrico; Heinemann, Stefan H; Kandt, Christian; Imhof, Diana

    2014-12-15

    The oxidation of the conotoxin ?-SIIIA in different ionic liquids was investigated, and the results were compared with those obtained in [C2 mim][OAc]. Conversion of the reduced precursor into the oxidized product was observed in the protic ILs methyl- and ethylammonium formate (MAF and EAf, respectively), whereas choline dihydrogenphosphate and Ammoeng 110 failed to yield folded peptide. However, the quality and yield of the peptide obtained in MAF and EAF were lower than in the case of the product from [C2 mim][OAc]. Reaction conditions (temperature, water content) also had an impact on peptide conversion. A closer look at the activities of ?-SIIIA versions derived from an up-scaled synthesis in [C2 mim][OAc] revealed a significant loss of the effect on ion channel NaV 1.4 relative to the buffer-oxidized peptide, whereas digestion of either ?-SIIIA product by trypsin was unaffected. This was attributed to adherence of ions from the IL to the peptide, because the disulfide connectivity is basically the same for the differentially oxidized ?-SIIIA versions. PMID:25376613

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

    PubMed

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

    2015-12-01

    A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications. PMID:26505641

  4. Decoupling of charge transport from structural dynamics in protic ionic liquids

    NASA Astrophysics Data System (ADS)

    Sangoro, Joshua; Sokolov, Alexei; Kremer, Friedrich; Paluch, Marian

    2013-03-01

    Broadband dielectric spectroscopy, differential scanning calorimetry and rheology are employed to investigate charge transport and dynamics in protic and aprotic ionic liquids. While the structural ?-relaxation rates and the characteristic charge diffusion rates coincide for aprotic ionic liquids, the latter is found to be more than 100 times for the protic ionic liquids studied. Moreover, the analysis of protic ionic liquids revealed a decoupling of temperature dependence of ionic transport from that of structural relaxation with the degree of decoupling increasing with fragility of the liquid. The potential technological impact of these results will be discussed.

  5. The synthesis and electrochemical characterization of bis(fluorosulfonyl)imide-based protic ionic liquids.

    PubMed

    Menne, S; Vogl, T; Balducci, A

    2015-02-28

    A protic ionic liquid containing the FSI anion has been synthesized for the first time and used as an electrolyte in an electrochemical storage device. This PIL-based electrolyte outperforms commonly used aprotic ionic liquids, maintaining the advantages and safety of ionic liquid-based electrolytes. PMID:25645883

  6. 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.

  7. Hydrogen bonding in ionic liquids.

    PubMed

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-01

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (?BCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H ?* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak through to very strong H-bonds. PMID:25582457

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

    SciTech Connect

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

    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.

  9. Photorheological ionic liquids.

    PubMed

    Av, Joo; Cidade, M T; Rodriguez, Vincent; Lima, Joo C; Parola, A Jorge

    2015-06-01

    Two room temperature ionic liquids (ILs) bearing coumarin and p-hydroxycinnamic acid moieties are synthesized, and their photochemistry is studied in solution and neat conditions. Irradiation at absorption maxima leads to photochemical transformations and results in changes of their rheological properties which are evaluated by rotational rheometry. Samples of ionic liquids are also studied by Hyper-Rayleigh scattering, and the effect of their photochemistry on ionic nanoaggregation is discussed. PMID:25970078

  10. 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

  11. Synthesis of ionic liquids

    DOEpatents

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

    2008-09-09

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

  12. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng (Knoxville, TN); Luo, Huimin (Knoxville, TN)

    2011-11-01

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

  13. Dissociation of equimolar mixtures of aqueous carboxylic acids in ionic liquids: role of specific interactions.

    PubMed

    Shukla, Shashi Kant; Kumar, Anil

    2015-04-30

    Hammett acidity function observes the effect of protonation/deprotonation on the optical density/absorbance of spectrophotometric indicator. In this work, the Hammett acidity, H0, of equimolar mixtures of aqueous HCOOH, CH3COOH, and CH3CH2COOH was measured in 1-methylimidazolium-, 1-methylpyrrolidinium-, and 1-methylpiperidinium-based protic ionic liquids (PILs) and 1-butyl-3-methylimidazolium-based aprotic ionic liquid (AIL) with formate (HCOO(-)) anion. Higher H0 values were observed for the equimolar mixtures of aqueous carboxylic acids in protic ionic liquids compared with those of the aprotic ionic liquid because of the involvement of the stronger specific interactions between the conjugate acid of ionic liquid and conjugate base of carboxylic acids as suggested by the hard-soft acid base (HSAB) theory. The different H0 values for the equimolar mixtures of aqueous carboxylic acids in protic and aprotic ionic liquids were noted to depend on the activation energy of proton transfer (Ea,H(+)). The higher activation energy of proton transfer was obtained in AIL, indicating lower ability to form specific interactions with solute than that of PILs. Thermodynamic parameters determined by the "indicator overlapping method" further confirmed the involvement of the secondary interactions in the dissociation of carboxylic acids. On the basis of the thermodynamic parameter values, the potential of different ionic liquids in the dissociation of carboxylic acids was observed to depend on the hydrogen bond donor acidity (α) and hydrogen bond acceptor basicity (β), characteristics of specific interactions. PMID:25839210

  14. 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

  15. Void-Assisted Ion-Paired Proton Transfer at WaterIonic Liquid Interfaces

    PubMed Central

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

    2015-01-01

    At the watertrihexyl(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

  16. Ionic liquid ethanol sensor.

    PubMed

    Lee, Yuan Gee; Chou, Tse-Chuan

    2004-07-30

    Ionic liquids containing lithium methylsulfonyl group were prepared from the precursors poly(propylene glycol)-block-(ethylene glycol)-block-(propylene glycol)-bis(2-aminopropyl ether) with different molecular weight. These liquids revealed excellent electrical conductivity in the temperature range -25 to 85 degrees C. Also, they exhibited a high boiling temperature and hence a low vapor pressure in ambient condition. Additionally, they showed a high fluidity with their viscosities being comparative with that of water. To determine the sensitivity of an ethanol sensor by using these ionic liquids, these liquids were subjected into a sequential electrochemical tests with nickel electrodes which performed a high sensitivity for the ethanol sensor. It was found that only the derivative with low molecular weight could detect ethanol. Furthermore, a linear relationship between the response current and the concentration of ethanol was constructed. The detection limit was found to be 0.13% (v/v) and its response time was 336 s. PMID:15142574

  17. Ionic liquids in chemical engineering.

    PubMed

    Werner, Sebastian; Haumann, Marco; Wasserscheid, Peter

    2010-01-01

    The development of engineering applications with ionic liquids stretches back to the mid-1990s when the first examples of continuous catalytic processes using ionic liquids and the first studies of ionic liquid-based extractions were published. Ever since, the use of ionic liquids has seen tremendous progress in many fields of chemistry and engineering, and the first commercial applications have been reported. The main driver for ionic liquid engineering applications is to make practical use of their unique property profiles, which are the result of a complex interplay of coulombic, hydrogen bonding and van der Waals interactions. Remarkably, many ionic liquid properties can be tuned in a wide range by structural modifications at their cation and anion. This review highlights specific examples of ionic liquid applications in catalysis and in separation technologies. Additionally, the application of ionic liquids as working fluids in process machines is introduced. PMID:22432579

  18. Pressure-induced mesoscopic disorder in protic ionic liquids: first computational study.

    PubMed

    Mariani, A; Caminiti, R; Campetella, M; Gontrani, L

    2016-01-20

    It has been recently shown that pressure may affect the mesoscopic heterogeneity in aprotic ionic liquids, owing to the long alkyl chain folding on itself. Here we explore protic ionic liquids, using classical molecular dynamics. These compounds have shorter and stiffer alkyl chains, harder to fold. We observed that high pressure affects the mesoscopic structure of the studied chemicals and, indeed, the effect may be ascribed to chain folding. PMID:26727054

  19. 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 (Rm?pip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmm?pip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmm?pip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmm?pip]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

  20. 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.

  1. Electrowetting of ionic liquids.

    PubMed

    Millefiorini, Stefano; Tkaczyk, Alan H; Sedev, Rossen; Efthimiadis, Jim; Ralston, John

    2006-03-01

    We have successfully demonstrated that imidazolium- and pyrrolidinium-based commercial room-temperature ionic liquids can electrowet (with a dc voltage) a smooth fluoropolymer (Teflon AF1600) surface. Qualitatively, the process is analogous to the electrowetting of aqueous electrolyte solutions: the contact angle versus voltage curve has a parabolic shape which saturates at larger voltages (positive or negative). On the other hand we observed several peculiarities: (i) the efficiency is significantly lower (by about an order of magnitude); (ii) the influence of the bulky cation is larger and the importance of the smaller anion is lesser, especially with respect to electrowetting saturation; (iii) there is an asymmetry in the saturation contact angles found for positive and negative voltages. The asymmetry may be correlated with the cation-anion asymmetry of the ionic liquids. The low efficiency may be caused by the presence of water and other impurities in these commercial materials. PMID:16506791

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

    DOEpatents

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

    2015-12-08

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

  4. 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

  5. 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 Brnsted 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

  6. Particle self-assembly at ionic liquid-based interfaces.

    PubMed

    Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

    2014-04-01

    This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated. PMID:24230971

  7. 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.

  8. 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.

  9. Hydrophobic ionic liquids

    DOEpatents

    Koch, Victor R. (Lincoln, MA); Nanjundiah, Chenniah (Lynn, MA); Carlin, Richard T. (Nashua, NH)

    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.

  10. Additive polarizabilities in ionic liquids.

    PubMed

    Bernardes, Carlos E S; Shimizu, Karina; Lopes, Jos Nuno Canongia; Marquetand, Philipp; Heid, Esther; Steinhauser, Othmar; Schrder, Christian

    2016-01-21

    An extended designed regression analysis of experimental data on density and refractive indices of several classes of ionic liquids yielded statistically averaged atomic volumes and polarizabilities of the constituting atoms. These values can be used to predict the molecular volume and polarizability of an unknown ionic liquid as well as its mass density and refractive index. Our approach does not need information on the molecular structure of the ionic liquid, but it turned out that the discrimination of the hybridization state of the carbons improved the overall result. Our results are not only compared to experimental data but also to quantum-chemical calculations. Furthermore, fractional charges of ionic liquid ions and their relation to polarizability are discussed. PMID:26675139

  11. Ionic Liquid Epoxy Resin Monomers

    NASA Technical Reports Server (NTRS)

    Paley, Mark S. (Inventor)

    2013-01-01

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

  12. 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.

  13. Solid-liquid interfaces of ionic liquid solutionsInterfacial layering and bulk correlations

    NASA Astrophysics Data System (ADS)

    Mezger, Markus; Roth, Roland; Schrder, 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.

  14. Solid-liquid interfaces of ionic liquid solutions--Interfacial layering and bulk correlations.

    PubMed

    Mezger, Markus; Roth, Roland; Schrder, Heiko; Reichert, Peter; Pontoni, Diego; Reichert, Harald

    2015-04-28

    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. PMID:25933784

  15. Solvent-mediated molar conductivity of protic ionic liquids.

    PubMed

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

    2015-01-01

    The molar conductivity, ?m, of protic ionic liquids (PILs) in molecular solvents is measured at 298.15 K. The decrease in the ?m values of PILs is observed with an increase in the concentration of PILs. The limiting molar conductivities, ?m(0), were obtained for each PIL in different molecular solvents using a least squares method. The ?m(0) data for PILs were correlated with the structural aspects of PILs and solvent properties. The polar protic solvents show poor ionic association as compared to the polar aprotic solvents, which is discussed on the basis of the hydrogen bond donating (HBD) ability of solvents and PILs. The alkyl chain substitution of anions plays a significant role in the ionic association of the PILs. The diffusion coefficient D(0) and the transport number t were determined, which were consistent with the ?m(0) values of PILs in water. The ?m(0) and D(0) values are dependent on the hydrodynamic radius of anions of these ionic liquids. The extent of ionic association for each PIL was discussed using temperature dependent ?m data for aqueous PIL systems in terms of the Walden plot. PMID:25406387

  16. Aqueous Brnsted-Lowry Chemistry of Ionic Liquid Ions.

    PubMed

    Driver, Gordon W

    2015-08-01

    Ionic liquids have become commonplace materials found in research laboratories the world over, and are increasingly utilised in studies featuring water as co-solvent. It is reported herein that proton activities, aH (+) , originating from auto-protolysis of H2O molecules, are significantly altered in mixtures with common ionic liquids comprised of Cl(-), [HSO4 ](-), [CH3SO4 ](-), [CH3COO](-), [BF4](-), relative to pure water. paH (+) values, recorded in partially aqueous media as -log(aH (+)), are observed over a wide range (?0-13) as a result of hydrolysis (or acid dissociation) of liquid salt ions to their associated parent molecules (or conjugate bases). Brnsted-Lowry acid-base character of ionic liquid ions observed is rooted in equilibria known to govern the highly developed aqueous chemistry of classical organic and inorganic salts, as their well-known aqueous pKs dictate. Classical salt behaviour observed for both protic and aprotic ions in the presence of water suggests appropriate attention need be given to relevant chemical systems in order to exploit, or avoid, the nature of the medium formed. PMID:26097128

  17. Elucidation of ionic interactions in the protic ionic liquid solutions by isothermal titration calorimetry.

    PubMed

    Rai, Gitanjali; Kumar, Anil

    2014-04-17

    The strong hydrogen-bonded network noted in protic ionic liquids (PILs) may lead to stronger interactions of the ionic entities of PILs with solvents (water, methanol, ethylene glycol, dimethylsulfoxide (DMSO), N,N'-dimethylformamide (DMF)) as compared with those of aprotic ionic liquids (APILs). The PILs used in this work are 1-methylimidazolium tetrafluoroborate, 2-methylpyridinium tetrafluoroborate, and N-methylpyrrolodinium tetrafluoroborate in comparison to 1-butyl-3-methylimidazolium tetrafluoroborate, which is classified as an APIL. In this work, the excess partial molar enthalpy, H(E)IL obtained from isothermal calorimetric titrations at 298.15 K is used to probe the nature of interactions of the PIL cations with solvent molecules against those present in APIL-solvent systems. This work also reports interesting flip-flopping in the thermal behavior of these PIL-solvent systems depending upon the structure of the cationic ring of a PIL. In some cases, these flip-flops are the specific fingerprints for specific PILs in a common solvent environment. The excess partial molar enthalpy at infinite dilution, H(E,?)IL, of these PILs bears a critical dependence on the solvent properties. An analysis of relative apparent molar enthalpies, ?L, of the PIL solutions by the ion interaction model of Pitzer yields important information on ionic interactions of these systems. PMID:24650134

  18. Ionic liquids in surface electrochemistry.

    PubMed

    Liu, Hongtao; Liu, Yang; Li, Jinghong

    2010-02-28

    Ionic liquids (IL) are widely used in electrochemistry due to their excellent properties such as good ionic conductivity, wide electrochemical potential window, high viscosity, high thermal stability, wide liquid range and tunable solvent properties. In electrochemistry, the performance of an electrochemical system is dependent on the properties of the interface at the IL/electrode. This review presents the surface electrochemistry in ILs, and the interfacial structures of IL/electrode and heterogeneous electron-transfer kinetics are detailed. Finally, the updated researches on the electrochemical applications of ILs such as electrode deposition, electrosynthesis, electrocatalysis, electrochemical biosensing, electrochemical capacitor and lithium batteries are demonstrated. PMID:20145833

  19. Ion pairing in ionic liquids

    NASA Astrophysics Data System (ADS)

    Kirchner, Barbara; Malberg, Friedrich; Firaha, Dzmitry S.; Hollczki, Oldamur

    2015-11-01

    In the present article we briefly review the extensive discussion in literature about the presence or absence of ion pair-like aggregates in ionic liquids. While some experimental studies point towards the presence of neutral subunits in ionic liquids, many other experiments cannot confirm or even contradict their existence. Ion pairs can be detected directly in the gas phase, but no direct method is available to observe such association behavior in the liquid, and the corresponding indirect experimental proofs are based on such assumptions as unity charges at the ions. However, we have shown by calculating ionic liquid clusters of different sizes that assuming unity charges for ILs is erroneous, because a substantial charge transfer is taking place between the ionic liquid ions that reduce their total charge. Considering these effects might establish a bridge between the contradicting experimental results on this matter. Beside these results, according to molecular dynamics simulations the lifetimes of ionion contacts and their joint motions are far too short to verify the existence of neutral units in these materials.

  20. Glyme-lithium salt equimolar molten mixtures: concentrated solutions or solvate ionic liquids?

    PubMed

    Ueno, Kazuhide; Yoshida, Kazuki; Tsuchiya, Mizuho; Tachikawa, Naoki; Dokko, Kaoru; Watanabe, Masayoshi

    2012-09-13

    To demonstrate a new family of ionic liquids (ILs), i.e., "solvate" ionic liquids, the properties (thermal, transport, and electrochemical properties, Lewis basicity, and ionicity) of equimolar molten mixtures of glymes (triglyme (G3) and tetraglyme (G4)) and nine different lithium salts (LiX) were investigated. By exploring the anion-dependent properties and comparing them with the reported data on common aprotic ILs, two different classes of liquid regimes, i.e., ordinary concentrated solutions and "solvate" ILs, were found in the glyme-Li salt equimolar mixtures ([Li(glyme)]X) depending on the anionic structures. The class a given [Li(glyme)]X belonged to was governed by competitive interactions between the glymes and Li cations and between the counteranions (X) and Li cations. [Li(glyme)]X with weakly Lewis basic anions can form long-lived [Li(glyme)](+) complex cations. Thus, they behaved as typical ionic liquids. The lithium "solvate" ILs based on [Li(glyme)]X have many desirable properties for lithium-conducting electrolytes, including high ionicity, a high lithium transference number, high Li cation concentration, and high oxidative stability, in addition to the common properties of ionic liquids. The concept of "solvate" ionic liquids can be utilized in an unlimited number of combinations of other metal salts and ligands, and will thus open a new field of research on ionic liquids. PMID:22897246

  1. PEROXIDASE ACTIVITY IN IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  2. 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.

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

    PubMed

    Tariq, Mohammad; Freire, Mara G; Saramago, Benilde; Coutinho, Joo A P; Lopes, Jos N Canongia; Rebelo, Lus Paulo N

    2012-01-21

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

  4. Ionic Liquids in Biomass Processing

    NASA Astrophysics Data System (ADS)

    Tan, Suzie Su Yin; Macfarlane, Douglas R.

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

  5. 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

  6. 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

  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. Amphiphilic and phase-separable ionic liquids for biomass processing.

    PubMed

    Holding, Ashley J; Heikkil, Mikko; Kilpelinen, Ilkka; King, Alistair W T

    2014-05-01

    One main limiting factor for the technoeconomics of future bioprocesses that use ionic liquids (ILs) is the recovery of the expensive and potentially toxic IL. We have demonstrated a new series of phase-separable ionic liquids, based on the hydrophobic tetraalkylphosphonium cation ([PRRRR](+)), that can dissolve lignin in the neat state but also hemicellulose and high-purity cellulose in the form of their electrolyte solutions with dipolar aprotic solvents. For example, the IL trioctylmethylphosphonium acetate ([P8881][OAc]) was demonstrated to dissolve up to 19?wt?% of microcrystalline cellulose (MCC) at 60?C with the addition of 40?wt?% of DMSO. It was found that the MCC saturation point is dependent on the molar ratio of DMSO and IL in solution. At the optimum saturation, a ?1:1 molar ratio of [P8881][OAc] to anhydroglucose units is observed, which demonstrates highly efficient solvation. This is attributed to the positive contribution that these more amphiphilic cation-anion pairs provide, in the context of the Lindman hypothesis. This effective dissolution is further illustrated by solution-state HSQC?NMR spectroscopy on MCC. Finally, it is also demonstrated that these electrolytes are phase separable by the addition of aqueous solutions. The addition of 10?% NaOAc solution allows a near quantitative recovery of high-purity [P8881][OAc]. However, increased volumes of aqueous solution reduced the recovery. The regenerated material was found to partially convert into the cellulose?II crystalline polymorph. PMID:24616349

  10. Effects of hydrophobic aggregation on the charge transport mechanism of quaternary ammonium ionic liquids

    NASA Astrophysics Data System (ADS)

    Griffin, Philip; Holt, Adam; Wang, Yangyang; Novikov, Vladimir; Sangoro, Joshua; Sokolov, Alexei

    2014-03-01

    Aprotic quaternary ammonium ionic liquids (ILs) are an important class of ILs due to their large electrochemical window and hydrophobicity. However, many of these ILs suffer from relatively low conductivity at room temperature which limits their use in electrochemical applications. In order to understand the nature of this low conductivity and its relation to the chemical structure of the alkyl ammonium cation, we have measured the charge transport properties and structural dynamics of the room temperature ionic liquid methyltrioctylammonium bistriflimide [m3oa][ntf2] over a broad temperature range using dielectric spectroscopy, dynamic light scattering, rheology, and pulsed field gradient nuclear magnetic resonance. We demonstrate that the low values of dc conductivity are due to the combined effects of significantly reduced ion mobility as well as reduced free ion concentration relative to other types of ILs. Secondly we find evidence for a mesoscopic scale structural relaxation process that we attribute to the reorientational motion of nanometer sized alkyl nanodomains. These two findings indicate that hydrophobic aggregation plays an important role in the charge transport mechanism of aprotic ammonium ionic liquids with long aliphatic side chains.

  11. 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.

  12. Surface orientation in ionic liquids

    NASA Astrophysics Data System (ADS)

    Law, George; Watson, Philip R.

    2001-09-01

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

  13. Membrane separation of ionic liquid solutions

    DOEpatents

    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.

  14. 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.

  15. 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

  16. 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.

  17. Mixtures of protic ionic liquids and propylene carbonate as advanced electrolytes for lithium-ion batteries.

    PubMed

    Vogl, T; Menne, S; Balducci, A

    2014-12-01

    In this study we investigated the chemical-physical properties of mixtures containing the protic ionic liquid (PIL) N-butyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYRH4TFSI), propylene carbonate (PC) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in view of their use as electrolytes for lithium-ion batteries (LIBs). We showed that these electrolytic solutions might display conductivity and viscosity comparable to those of conventional electrolytes. Depending on the amount of PIL present inside the mixtures, such mixtures might also display the ability to suppress the anodic dissolution of Al. Furthermore, we showed that the coordination of lithium ions by TFSI in PIL-PC mixtures appears to be different than the one observed for mixtures of PC and aprotic ionic liquids (AILs). When used in combination with a battery electrode, e.g. lithium iron phosphate (LFP), these mixtures allow the achievement of high performance also at a very high C-rate. PMID:25328075

  18. 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.

  19. A quantitative ionicity scale for liquid chloride salts.

    PubMed

    Ingman, Petri; Driver, Gordon W

    2012-10-01

    Knowledge of ionicity is requisite for successful identification of those salt qualities required to design and couple the most appropriate fluid for performance of an intended chemical function. We report on utilisation of (35)Cl(-) quadrupolar coupling constants (C(Q)) to quantitatively assess the ionicities of given chloride salts, by exploiting the electronic response of the quadrupolar chlorine atom as a function of its immediate chemical environment. We find that protic salts in particular, like their aprotic analogues, are highly ionised, while at the same time being highly associated, in stark contrast to literature reports claiming in general that they are of sub-ionic origin. PMID:22886109

  20. Photochemical Schiemann Reaction in Ionic Liquids

    PubMed Central

    Heredia-Moya, Jorge; Kirk, Kenneth L.

    2007-01-01

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

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

    PubMed

    Shi, Xianzhe; Qiao, Lizhen; Xu, Guowang

    2015-11-13

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

  2. Ionic liquid pillar[5]arene: its ionic conductivity and solvent-free complexation with a guest.

    PubMed

    Ogoshi, Tomoki; Ueshima, Naosuke; Yamagishi, Tada-aki; Toyota, Yoshiyuki; Matsumi, Noriyoshi

    2012-04-11

    A room-temperature ionic liquid containing macrocyclic compound pillar[5]arene in its core was synthesized. The ionic liquid showed high thermal stability, moderate ionic conductivity and solvent-free complexation ability with the guest tetracyanoethylene. PMID:22377801

  3. 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

  4. 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.

  5. Phosphonium-based ionic liquids and uses

    DOEpatents

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

    2014-12-30

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

  6. 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.

  7. Supramolecular Ionic-Liquid Gels with High Ionic Conductivity.

    PubMed

    Maravelski, Aleksandra; Smre?ki, Vilko; Vianello, Robert; ini?, Mladen; Mogu-Milankovi?, Andrea; anti?, Ana

    2015-08-17

    Supramolecular ionogels were prepared by the gelation of room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4 ]) with (S,S)-bis(leucinol)oxalamide. Remarkably, the ionic conductivity of solutions and ionogels with low gelator concentrations is higher than that of neat [BMIm][BF4 ]. On the basis of molecular dynamics simulations and quantum mechanical calculations, the origin of this phenomenon is attributed to the higher affinity of gelator molecules towards [BF4 ](-) ions, which reduces the electrostatic attraction between [BMIm](+) and [BF4 ](-) and thus increases their mobility. With increasing gelator concentration, the ionic conductivity decreases due to the formation of a denser gelator matrix, which hinders the pathways for ionic transport. However, even for very dense ionogels, this decrease is less than one order of magnitude relative to neat [BMIm][BF4 ], and thus they can be classified as highly conductive materials with strong potential for application as functional electrolytes. PMID:26178864

  8. Materials Named Ionic LiquidsHistory and Definition

    NASA Astrophysics Data System (ADS)

    Hirayama, Naoki

    In recent years, a series of materials named ionic liquids have attracted attention and been extensively studied in various fields of chemistry. What ionic liquids are, however, has not been yet standardized. This review presents the history of ionic liquid research and definition of the term ionic liquid from a viewpoint that it should be classified as a nonaqueous solvent.

  9. New electrolytes for aluminum production: Ionic liquids

    NASA Astrophysics Data System (ADS)

    Zhang, Mingming; Kamavarum, Venkat; Reddy, Ramana G.

    2003-11-01

    In this article, the reduction, refining/recycling, and electroplating of aluminum from room-temperature molten salts are reviewed. In addition, the characteristics of several non-conventional organic solvents, electrolytes, and molten salts are evaluated, and the applicability of these melts for production of aluminum is discussed with special attention to ionic liquids. Also reviewed are electrochemical processes and conditions for electrodeposition of aluminum using ionic liquids at near room temperatures.

  10. The Solubility Parameters of Ionic Liquids

    PubMed Central

    Marciniak, Andrzej

    2010-01-01

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

  11. 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.

  12. Aqueous Solutions of Ionic Liquids: Microscopic Assembly.

    PubMed

    Vicent-Luna, Jose Manuel; Dubbeldam, David; Gmez-lvarez, Paula; Calero, Sofia

    2016-02-01

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

  13. 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 liquidsa 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.

  14. 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

  15. Vesicles and reverse vesicles of an ionic liquid in ionic liquids.

    PubMed

    Rao, K Srinivasa; So, Soonyong; Kumar, Arvind

    2013-09-21

    First evidence and the mechanism of formation of closed bilayer structures by a single chain amino acid ionic liquid (IL), L-proline isopropylester laurylsulfate in both hydrophilic and hydrophobic ILs, is reported. Such ionic self-assemblies are shown to be guided by fine balance of solvophobic effects and ionic arrangements via hydrogen bonding and electrostatic interactions. PMID:23917547

  16. Adsorbed and near surface structure of ionic liquids at a solid interface.

    PubMed

    Segura, Juan Jos; Elbourne, Aaron; Wanless, Erica J; Warr, Gregory G; Votchovsky, Kislon; Atkin, Rob

    2013-03-01

    The structure of solid-ionic liquid (IL) interfaces has been characterised with unprecedented clarity by employing a range of atomic force microscopy (AFM) imaging techniques and tip pressures appropriate for the system under study. Soft contact and amplitude-modulation (AM) AFM imaging have been used to elucidate the lateral structure of ILs adsorbed onto mica, and in the near surface ion layers. Data is presented for ethylammonium nitrate (EAN) and 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)imide (EMIm TFSI). Whereas EAN is a protic IL that forms a nanostructured sponge phase in the bulk, EMIm TFSI is aprotic and has weak (or absent) bulk association structure. Comparison of results obtained for the two liquids elucidates how the strength of bulk liquid morphology effects lateral organisation at the surface, and any effect of IL class, i.e. protic versus aprotic. Imaging reveals EAN self assembles at the solid surface in a worm-like morphology, whereas EMIm cations adsorb in a more isolated fashion, but still in rows templated by the mica surface. To the authors' knowledge, the wormlike structures present at the EAN-mica interface are the smallest self-assembled aggregates ever imaged on a solid surface. PMID:23361257

  17. 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.

  18. ELECTROCHEMICAL STUDIES OF HEMIN IN IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  19. Isotachophoretic separation of selected imidazolium ionic liquids.

    PubMed

    Kosobucki, Przemys?aw; Buszewski, Bogus?aw

    2008-02-15

    Results of determination of selected imidazolium ionic liquids by isotachophoresis (ITP) with conductometric detection was presented. The effects of the molar mass of different ionic liquids on electrophoretic mobility was observed. The presented method was validated and basic validation parameters were determined. Limit of detection (LOD) in a 10 and 25ng/L for anions and cations, respectively, is very satisfied. Thanks to its low cost and high rate, the presented method can be used in qualitative routine analysis as an alternative technique to liquid chromatography. PMID:18371834

  20. Mixtures of protic ionic liquids and molecular cosolvents: a molecular dynamics simulation.

    PubMed

    Docampo-Álvarez, Borja; Gómez-González, Víctor; Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

    2014-06-01

    In this work, the effect of molecular cosolvents (water, ethanol, and methanol) on the structure of mixtures of these compounds with a protic ionic liquid (ethylammonium nitrate) is analyzed by means of classical molecular dynamics simulations. Included are as-yet-unreported measurements of the densities of these mixtures, used to test our parameterized potential. The evolution of the structure of the mixtures throughout the concentration range is reported by means of the calculation of coordination numbers and the fraction of hydrogen bonds in the system, together with radial and spatial distribution functions for the various molecular species and molecular ions in the mixture. The overall picture indicates a homogeneous mixing process of added cosolvent molecules, which progressively accommodate themselves in the network of hydrogen bonds of the protic ionic liquid, contrarily to what has been reported for their aprotic counterparts. Moreover, no water clustering similar to that in aprotic mixtures is detected in protic aqueous mixtures, but a somehow abrupt replacing of [NO3](-) anions in the first hydration shell of the polar heads of the ionic liquid cations is registered around 60% water molar concentration. The spatial distribution functions of water and alcohols differ in the coordination type, since water coordinates with [NO3](-) in a bidentate fashion in the equatorial plane of the anion, while alcohols do it in a monodentate fashion, competing for the oxygen atoms of the anion. Finally, the collision times of the different cosolvent molecules are also reported by calculating their velocity autocorrelation functions, and a caging effect is observed for water molecules but not in alcohol mixtures. PMID:24908021

  1. Mixtures of protic ionic liquids and molecular cosolvents: A molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Docampo-Álvarez, Borja; Gómez-González, Víctor; Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R.; Cabeza, Óscar; Gallego, Luis J.; Varela, Luis M.

    2014-06-01

    In this work, the effect of molecular cosolvents (water, ethanol, and methanol) on the structure of mixtures of these compounds with a protic ionic liquid (ethylammonium nitrate) is analyzed by means of classical molecular dynamics simulations. Included are as-yet-unreported measurements of the densities of these mixtures, used to test our parameterized potential. The evolution of the structure of the mixtures throughout the concentration range is reported by means of the calculation of coordination numbers and the fraction of hydrogen bonds in the system, together with radial and spatial distribution functions for the various molecular species and molecular ions in the mixture. The overall picture indicates a homogeneous mixing process of added cosolvent molecules, which progressively accommodate themselves in the network of hydrogen bonds of the protic ionic liquid, contrarily to what has been reported for their aprotic counterparts. Moreover, no water clustering similar to that in aprotic mixtures is detected in protic aqueous mixtures, but a somehow abrupt replacing of [NO3]- anions in the first hydration shell of the polar heads of the ionic liquid cations is registered around 60% water molar concentration. The spatial distribution functions of water and alcohols differ in the coordination type, since water coordinates with [NO3]- in a bidentate fashion in the equatorial plane of the anion, while alcohols do it in a monodentate fashion, competing for the oxygen atoms of the anion. Finally, the collision times of the different cosolvent molecules are also reported by calculating their velocity autocorrelation functions, and a caging effect is observed for water molecules but not in alcohol mixtures.

  2. 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

  3. 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.

  4. Polyester Spherulite Crystallization in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Singfield, Kathy; Mitchell, Shawna

    2009-03-01

    A series of polyesters have been crystallized in ionic liquids. Spherulites of the polyesters have been grown isothermally from different ionic liquids after cooling the single phase polymer/ionic liquid system from above the polymer melting point temperature. To the authors' best knowledge this is the first reported account of polyester spherulites grown from these non-traditional solvents. The combination of physical properties of the crystallizing system supports the un-restrained branching/splitting volume-filling growth in all radial directions of the suspended crystallizing entity. The morphology of the collected spherulites at various stages of their formation was examined using scanning electron microscopy (SEM). The SEM results provide a clear visual inspection of the early-stage growth forms and the branching/splitting patterns involved in their evolution to the final spherical form.

  5. 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.

  6. Unravelling nanoconfined films of ionic liquids

    SciTech Connect

    Lee, Alpha A.; Vella, Dominic; Goriely, Alain; Perkin, Susan

    2014-09-07

    The confinement of an ionic liquid between charged solid surfaces is treated using an exactly solvable 1D Coulomb gas model. The theory highlights the importance of two dimensionless parameters: the fugacity of the ionic liquid, and the electrostatic interaction energy of ions at closest approach, in determining how the disjoining pressure exerted on the walls depends on the geometrical confinement. Our theory reveals that thermodynamic fluctuations play a vital role in the squeezing out of charged layers as the confinement is increased. The model shows good qualitative agreement with previous experimental data, with all parameters independently estimated without fitting.

  7. 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...

  8. VOC and HAP recovery using ionic liquids

    SciTech Connect

    Michael R. Milota : Kaichang Li

    2007-05-29

    During the manufacture of wood composites, paper, and to a lesser extent, lumber, large amounts of volatile organic compounds (VOCs) such as terpenes, formaldehyde, and methanol are emitted to air. Some of these compounds are hazardous air pollutants (HAPs). The air pollutants produced in the forest products industry are difficult to manage because the concentrations are very low. Presently, regenerative thermal oxidizers (RTOs and RCOs) are commonly used for the destruction of VOCs and HAPs. RTOs consume large amounts of natural gas to heat air and moisture. The combustion of natural gas generates increased CO2 and NOx, which have negative implications for global warming and air quality. The aforementioned problems are addressed by an absorption system containing a room-temperature ionic liquid (RTIL) as an absorbent. RTILs are salts, but are in liquid states at room temperature. RTILs, an emerging technology, are receiving much attention as replacements for organic solvents in industrial processes with significant cost and environmental benefits. Some of these processes include organic synthesis, extraction, and metal deposition. RTILs would be excellent absorbents for exhausts from wood products facilities because of their unique properties: no measurable vapor pressure, high solubility of wide range of organic compounds, thermal stability to 200°C (almost 400°F), and immisciblity with water. Room temperature ionic liquids were tested as possible absorbents. Four were imidizolium-based and were eight phosphonium-based. The imidizolium-based ionic liquids proved to be unstable at the conditions tested and in the presence of water. The phosphonium-based ionic liquids were stable. Most were good absorbents; however, cleaning the contaminates from the ionic liquids was problematic. This was overcome with a higher temperature (120°C) than originally proposed and a very low pressure (1 kPa. Absorption trials were conducted with tetradecy(trihexyl)phosphonium dicyanamide as the RTIL. It was determined that it has good absorption properties for methanol and α-pinene, is thermally stable, and is relatively easy to synthesize. It has a density of 0.89 g/mL at 20°C and a molecular weight of 549.9 g/mol. Trials were conducted with a small absorption system and a larger absorption system. Methanol, formaldehyde, and other HAPs were absorbed well, nearly 100%. Acetaldehyde was difficult to capture. Total VOC capture, while satisfactory on methanol and α-pinene in a lab system, was less than expected in the field, 60-80%. The inability to capture the broad spectrum of total organics is likely due to difficulties in cleaning them from the ionic liquid rather than the ability of the ionic liquid to absorb. It’s likely that a commercial system could be constructed to remove 90 to 100% of the gas contaminates. Selecting the correct ionic liquid would be key to this. Absorption may not be the main selection criterion, but rather how easily the ionic liquid can be cleaned is very important. The ionic liquid absorption system might work very well in a system with a limited spectrum of pollutants, such as a paint spray line, where there are not very high molecular weight, non volatile, compounds in the exhaust.

  9. A room temperature spin crossover ionic liquid.

    PubMed

    Fitzpatrick, Anthony J; O'Connor, Helen M; Morgan, Grace G

    2015-12-28

    Two new paramagnetic ionic liquids (ILs) comprising a mononuclear iron(iii) or manganese(iii) complex cation, charge balanced by a dicyanamide anion are reported which show a range of spin states. Both are liquids at room temperature and the Fe(iii) based IL exhibits a spin crossover close to 300 K. The spin crossover profile is independent of the solvation, and is both air and moisture stable. PMID:26599842

  10. BIOELECTROCATALYTIC REACTIONS IN ROOM TEMPERATURE IONIC LIQUIDS

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  11. Reactions of Starch in Ionic Liquids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We found that starches are found to be soluble at 80 C 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...

  12. Thermoresponsive poly(ionic liquid) hydrogels.

    PubMed

    Zi?kowski, Bartosz; Diamond, Dermot

    2013-11-11

    A new series of LCST ILs have been copolymerised with crosslinkers of varying length to afford the first ever thermoresponsive poly(ionic liquid)-based hydrogels. These hydrogels exhibit surprisingly broad LCST and volume transition behaviour compared to standard thermoresponsive gels and linear ILs. PMID:24064665

  13. Ionic liquid electrolytes for reversible magnesium electrochemistry.

    PubMed

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

    2016-03-01

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

  14. 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

  15. Catalytic Alkene Metathesis in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Fischmeister, Cdric

    Olefin metathesis has found a tremendous number of application in the past 25 years. Immobilisation of olefin metathesis (pre)catalysts in room temperature ionic liquids (RTILs) offers the opportunity to recover and reuse the catalyst and also to reduce the level of ruthenium (Ru) contaminants in the products.

  16. 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.

  17. 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...

  18. 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.

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

    PubMed

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

    2003-02-21

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

  20. 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.

  1. Intermolecular dynamics in liquids studied by a third order nonlinear spectroscopy

    NASA Astrophysics Data System (ADS)

    Shirota, Hideaki

    2015-01-01

    Intermolecular dynamics, particularly intermolecular vibrational dynamics, in simple aprotic molecular liquids including both nonaromatic and aromatic molecular liquids measured using femtosecond Raman-induced Kerr effect spectroscopy is discussed. A correlation between the first moment of the intermolecular vibrational band and the value of the static physical properties, the square root of surface tension divided by liquid density, is shown. The data of the aprotic molecular liquids are also compared to that of room temperature ionic liquids.

  2. Poly(ethylene oxide) Mushrooms Adsorbed at Silica-Ionic Liquid Interfaces Reduce Friction.

    PubMed

    Sweeney, James; Webber, Grant B; Atkin, Rob

    2016-03-01

    The adsorbed layer conformation and lubricity of 35, 100, and 300 kDa PEO adsorbed to ionic liquid (IL)-silica interfaces from 0.01 wt % solutions have been investigated using colloid probe atomic force microscopy. The ILs used were propylammonium nitrate (PAN) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), which are protic and aprotic ILs, respectively. Normal force curves reveal steric interactions consistent with adsorbed polymer layers which are best fit using the mushroom model. Friction measurements show that the adsorbed polymer layer markedly reduces friction compared to surfaces sliding in the pure ILs and that lubricity increases with polymer length. When polymer is adsorbed to the sliding surfaces, friction is controlled by the creation and disruption of intermolecular interactions between entangled chains and the dragging of polymer chains through the interpenetration region. These experiments show that added polymer can reduce friction while maintaining the useful properties of ILs as lubricants. PMID:26844589

  3. Electrofluorochromism in ?-conjugated ionic liquid crystals

    NASA Astrophysics Data System (ADS)

    Beneduci, Amerigo; Cospito, Sante; La Deda, Massimo; Veltri, Lucia; Chidichimo, Giuseppe

    2014-01-01

    Materials in which photoluminescence is modulated by redox processes are known as electrofluorochromic. Intrinsically switchable fluorophores, incorporating both redox and fluorescent moieties, could be ideal electrofluorochromic materials if they possess high fluorescence quantum yields in at least one of their redox states. Fluorescent liquid crystals with redox active centres could combine the above requirements with the advantage to work in bulk anisotropic phases. However, electrofluorochromic liquid crystals have not been reported yet because their synthesis is challenging due to aggregation-caused fluorescent quenching. Here we show the first examples of electrofluorochromic ?-conjugated ionic liquid crystals based on thienoviologens. These ordered materials, combining ionic and electronic functions, are highly fluorescence in the bulk state (quantum yield>60%). Their direct electrochemical reduction leads to fast and reversible bulk electrofluorochromic response in both columnar and smectic phases allowing for fluorescence intensity modulation and colour tuning.

  4. Phase behavior of ionic liquid crystals

    NASA Astrophysics Data System (ADS)

    Kondrat, S.; Bier, M.; Harnau, L.

    2010-05-01

    Bulk properties of ionic liquid crystals are investigated using density functional theory. The liquid crystal molecules are represented by ellipsoidal particles with charges located in their center or at their tails. Attractive interactions are taken into account in terms of the Gay-Berne pair potential. Rich phase diagrams involving vapor, isotropic and nematic liquid, as well as smectic phases are found. The dependence of the phase behavior on various parameters such as the length of the particles and the location of charges on the particles is studied.

  5. 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.

  6. 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

  7. Structural Transitions at Ionic Liquid Interfaces.

    PubMed

    Rotenberg, Benjamin; Salanne, Mathieu

    2015-12-17

    Recent advances in experimental and computational techniques have allowed for an accurate description of the adsorption of ionic liquids on metallic electrodes. It is now well-established that they adopt a multilayered structure and that the composition of the layers changes with the potential of the electrode. In some cases, potential-driven ordering transitions in the first adsorbed layer have been observed in experiments probing the interface on the molecular scale or by molecular simulations. This perspective gives an overview of the current understanding of such transitions and of their potential impact on the physical and (electro)chemical processes at the interface. In particular, peaks in the differential capacitance, slow dynamics at the interface, and changes in the reactivity have been reported in electrochemical studies. Interfaces between ionic liquids and metallic electrodes are also highly relevant for their friction properties, the voltage-dependence of which opens the way to exciting applications. PMID:26722704

  8. Ionic Liquid Membranes for Carbon Dioxide Separation

    SciTech Connect

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

    2008-07-12

    Recent scientific studies are rapidly advancing novel technological improvements and engineering developments that demonstrate the ability to minimize, eliminate, or facilitate the removal of various contaminants and green house gas emissions in power generation. The Integrated Gasification Combined Cycle (IGCC) shows promise for carbon dioxide mitigation not only because of its higher efficiency as compared to conventional coal firing plants, but also due to a higher driving force in the form of high partial pressure. One of the novel technological concepts currently being developed and investigated is membranes for carbon dioxide (CO2) separation, due to simplicity and ease of scaling. A challenge in using membranes for CO2 capture in IGCC is the possibility of failure at elevated temperatures or pressures. Our earlier research studies examined the use of ionic liquids on various supports for CO2 separation over the temperature range, 37°C-300°C. The ionic liquid, 1-hexyl-3methylimidazolium Bis(trifluoromethylsulfonyl)imide, ([hmim][Tf2N]), was chosen for our initial studies with the following supports: polysulfone (PSF), poly(ether sulfone) (PES), and cross-linked nylon. The PSF and PES supports had similar performance at room temperature, but increasing temperature caused the supported membranes to fail. The ionic liquid with the PES support greatly affected the glass transition temperature, while with the PSF, the glass transition temperature was only slightly depressed. The cross-linked nylon support maintained performance without degradation over the temperature range 37-300°C with respect to its permeability and selectivity. However, while the cross-linked nylon support was able to withstand temperatures, the permeability continued to increase and the selectivity decreased with increasing temperature. Our studies indicated that further testing should examine the use of other ionic liquids, including those that form chemical complexes with CO2 based on amine interactions. The hypothesis is that the performance at the elevated temperatures could be improved by allowing a facilitated transport mechanism to become dominant. Several amine-based ionic liquids were tested on the cross-linked nylon support. It was found that using the amine-based ionic liquid did improve selectivity and permeability at higher temperature. The hypothesis was confirmed, and it was determined that the type of amine used also played a role in facilitated transport. Given the appropriate aminated ionic liquid with the cross-linked nylon support, it is possible to have a membrane capable of separating CO2 at IGCC conditions. With this being the case, the research has expanded to include separation of other constituents besides CO2 (CO, H2S, etc.) and if they play a role in membrane poisoning or degradation. This communication will discuss the operation of the recently fabricated ionic liquid membranes and the impact of gaseous components other than CO2 on their performance and stability.

  9. Self-propelled chemotactic ionic liquid droplets.

    PubMed

    Francis, Wayne; Fay, Cormac; Florea, Larisa; Diamond, Dermot

    2015-02-11

    Herein we report the chemotactic behaviour of self-propelled droplets composed solely of the ionic liquid trihexyl(tetradecyl)phosphonium chloride ([P(6,6,6,14)][Cl]). These droplets spontaneously move along an aqueous-air boundary in the direction of chloride gradients to specific destinations due to asymmetric release of [P(6,6,6,14)](+) cationic surfactant from the droplet into the aqueous phase. PMID:25562698

  10. Mirrorless dye doped ionic liquid lasers.

    PubMed

    Barna, Valentin; De Cola, Luisa

    2015-05-01

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

  11. Anharmonicity and Fragility of Protic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Kim, Jenny; Angell, Austen; Ueno, Kazuhide; Tyagi, Madhu; Soles, Christopher; Masser, Kevin

    2013-03-01

    Supercooled liquids are often characterized by their fragility which is associated with physicochemical properties. However, the origin of fragility is still controversial. Superfragile liquid, decahydroisoquinoline (DHiQ) is chosen as a parent molecule to systematically investigate the relationship between anharmonicity and fragility of supercooled liquids. Earlier study by Ueno et al. (J. Phys. Chem. B 2012, 116) demonstrated that the protonation of DHiQ by different Bronsted acids results in the loss of superfragility. To understand the nature of fragile liquids, we conducted inelastic/quasielastic (IE/QE) neutron scattering measurements to examine low frequency vibrational dynamics (boson peak) and the relaxation behavior of DHiQ (high fragility) and DHiQ-based ionic liquids with intermediate (formate, Fm) and low (trifluoromethansulfonimide, TFSI) fragilities. With the protonation, molecular acids will be hydrogen-deficient and the scattering will be dominated by cation, [DHiQ+]. This strategy simplifies our interpretation in terms of understanding the fitting result from IENS/QENS spectra. By protonating DHiQ with stronger acids, large shift in low frequency vibrational modes and smaller mean square displacements were examined at temperatures higher than Tg. We illustrate how the degree of protonation and ionicity plays a role in the loss in superfragility of DHiQ.

  12. A new proton conductive liquid with no ions: pseudo-protic ionic liquids.

    PubMed

    Doi, Hiroyuki; Song, Xuedan; Minofar, Babak; Kanzaki, Ryo; Takamuku, Toshiyuki; Umebayashi, Yasuhiro

    2013-08-26

    Liquids with no ions! Raman analysis and quantum calculations suggest that electrically neutral molecular species predominantly exist in an N-methylimidazole and acetic acid equimolar mixture, and that ionic species are rather minor. Nevertheless, the mixture has significant ionic conductivity, and shows "good ionic" or "superionic" behavior (see figure). It may be suitable to call such liquids "pseudo-ionic liquids" rather than "ionic liquids". PMID:23873834

  13. Insight into the cosolvent effect of cellulose dissolution in imidazolium-based ionic liquid systems.

    PubMed

    Zhao, Yuling; Liu, Xiaomin; Wang, Jianji; Zhang, Suojiang

    2013-08-01

    Recently, it has been reported that addition of a cosolvent significantly influences solubility of cellulose in ionic liquids (ILs), but little is known about the influence mechanism of the cosolvent on the molecular level. In this work, four kinds of typical molecular solvents (dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), CH?OH, and H?O) were used to investigate the effect of cosolvents on cellulose dissolution in [C?mim][CH?COO] by molecular dynamics simulations and quantum chemistry calculations. It was found that dissolution of cellulose in IL/cosolvent systems is mainly determined by the hydrogen bond interactions between [CH?COO](-) anions and the hydroxyl protons of cellulose. The effect of cosolvents on the solubility of cellulose is indirectly achieved by influencing such hydrogen bond interactions. The strong preferential solvation of [CH?COO](-) by the protic solvents (CH?OH and H?O) can compete with the cellulose-[CH?COO](-) interaction in the dissolution process, resulting in decreased cellulose solubility. On the other hand, the aprotic solvents (DMSO and DMF) can partially break down the ionic association of [C?mim][CH?COO] by solvation of the cation and anion, but no preferential solvation was observed. The dissociated [CH?COO](-) would readily interact with cellulose to improve the dissolution of cellulose. Furthermore, the effect of the aprotic solvent-to-IL molar ratio on the dissolution of cellulose in [C?mim][CH?COO]/DMSO systems was investigated, and a possible mechanism is proposed. These simulation results provide insight into how a cosolvent affects the dissolution of cellulose in ILs and may motivate further experimental studies in related fields. PMID:23829272

  14. 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.

  15. Liquid-liquid phase separation in solutions of ionic liquids: phase diagrams, corresponding state analysis and comparison with simulations of the primitive model

    NASA Astrophysics Data System (ADS)

    Schröer, W.; Vale, V. R.

    2009-10-01

    Phase diagrams of ionic solutions of the ionic liquid C18mim+NTF2- (1-n-octadecyl-3-methyl imidazolium bistrifluormethylsulfonylimide) in decalin, cyclohexane and methylcyclohexane are reported and compared with that of solutions of other imidazolium ionic liquids with the anions NTF2-, Cl- and BF4- in arenes, CCl4, alcohols and water. The phase diagrams are analysed presuming Ising criticality and taking into account the asymmetry of the phase diagrams. The resulting parameters are compared with simulation results for equal-sized charged hard spheres in a dielectric continuum, the restricted primitive model (RPM) and the primitive model (PM) that allows for ions of different size. In the RPM temperature scale the critical temperatures vary almost linearly with the dielectric permittivity of the solvent. The RPM critical temperatures of the solutions in non-polar solvents are very similar, somewhat below the RPM value. Correlations with the boiling temperatures of the solvents and a dependence on the length of the side chain of the imidazolium cations show that dispersion interactions modify the phase transition, which is mainly determined by Coulomb forces. Critical concentrations, widths of the phase diagrams and the slopes of the diameter are different for the solutions in protic and aprotic solvents. The phase diagrams of the solutions in alcohols and water get a lower critical solution point when represented in RPM variables.

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

    SciTech Connect

    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.

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

    PubMed

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

    2008-08-14

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

  18. 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

  19. 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.

  20. 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

  1. Application of ionic liquids in photopolymerizable holographic materials

    NASA Astrophysics Data System (ADS)

    Lin, Hechun; de Oliveira, Peter W.; Veith, Michael

    2011-04-01

    The influence of ionic liquids in photopolymerizable holographic materials was investigated extensively. The structures of ionic liquids have important effect on the properties of the materials. Although not all tested ionic liquids can improve the properties of the materials, the ionic liquids based on imidazolium, pyridium, or phosphonium with appropriate counter anions can be used as additives to increase the sensitivity, the diffraction efficiency, and the resolution of the materials in the thin hologram. Polymerizable ionic liquids have also been used as additives. Higher sensitivity, higher diffraction efficiency and higher resolution were obtained as well. These ionic liquids can carry out the photopolymerization during exposure to UV light to recording the hologram. They may assist to form a more stable hologram.

  2. Ionic liquids for soft functional materials with carbon nanotubes.

    PubMed

    Fukushima, Takanori; Aida, Takuzo

    2007-01-01

    A serendipitous finding that ionic liquids gel with carbon nanotubes has opened a new possibility of ionic liquids as modifiers for carbon nanotubes. Upon being ground into ionic liquids, carbon nanotube bundles are untangled, and the resultant fine bundles form a network structure. This is due to the possible specific interaction between the imidazolium ion component and the pi-electronic nanotube surface. The resultant gelatinous materials, consisting of highly electroconductive nanowires and fluid electrolytes, can be utilized for a wide variety of electrochemical applications, such as sensors, capacitors, and actuators. Ionic liquids allow for noncovalent and covalent modifications of carbon nanotubes and fabrication of polymer composites with enhanced physical properties. The processing of carbon nanotubes with ionic liquids is not accompanied by the disruption of the pi-conjugated nanotube structure and does not require solvents; therefore it can readily be scaled up. This article focuses on new aspects of ionic liquids for designer soft materials based on carbon nanotubes. PMID:17516613

  3. Electrotunable Lubricity with Ionic Liquid Nanoscale Films

    NASA Astrophysics Data System (ADS)

    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.

  4. 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

  5. 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

  6. Layering of ionic liquids on rough surfaces.

    PubMed

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

    2016-02-11

    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. PMID:26821595

  7. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Agrawal, Anoop (Tucson, AZ); Cronin, John P. (Tucson, AZ); Tonazzi, Juan C. L. (Tucson, AZ); Warner, Benjamin P. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM); Burrell, Anthony K. (Los Alamos, NM)

    2005-11-01

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

  8. Inhibition of amyloid formation by ionic liquids: ionic liquids affecting intermediate oligomers.

    PubMed

    Kalhor, Hamid Reza; Kamizi, Mostafa; Akbari, Jafar; Heydari, Akbar

    2009-09-14

    In searching for alternative ways to reduce or inhibit amyloid formation, we have studied this process using hen egg white lysozyme (HEWL) in the presence of a low concentration of protic ionic liquids. The ionic liquids were synthesized in a combinatorial fashion maintaining the cationic part (tetramethylguanidinium) with alteration of the anionic component of each compound tested. It was observed that one of these compounds (tetramethylguanidinium acetate) inhibited amyloid formation of HEWL in vitro by nearly 50%. Examination under transmission electron microscopy confirmed the fibril inhibition, and fibrils were observed to be morphologically thinner. To investigate the mechanism of inhibition, intrinsic fluorescence, ANS binding, and circular dichroism analyses were performed. These analyses indicated that the native structure of HEWL was maintained in the presence of the ionic liquid. Performing native PAGE and nondenaturing agarose electrophoresis, it became evident that some of the intermediate oligomers were not converted to protofibrils and that the oligomers were trapped in more stable conformations. Additionally, it was observed that this inhibitory effect was related to the ionic liquid itself and not the solvated ions. It also became evident that the carboxyl functional group was important in the inhibition. The size of the anions and kosmotropicity did not play significant roles in the fibril inhibition. PMID:19678699

  9. 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.

  10. 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.

  11. Highly luminescent and color-tunable salicylate ionic liquids

    SciTech Connect

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

    2014-03-11

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

  12. 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.

  13. Properties of Water Confined in Ionic Liquids

    PubMed Central

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

    2015-01-01

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

  14. Toxicity of ionic liquids prepared from biomaterials.

    PubMed

    Gouveia, W; Jorge, T F; Martins, S; Meireles, M; Carolino, M; Cruz, C; Almeida, T V; Arajo, M E M

    2014-06-01

    In search of environmentally-friendly ionic liquids (ILs), 14 were prepared based on the imidazolium, pyridinium and choline cations, with bromide and several amino acids as anions. Good yields were obtained in the synthesis of pyridinium ILs and those prepared from choline and amino acids. Four of the ILs synthesized from choline and the amino acids arginine, glutamine, glutamic acid and cystine are described here for the first time. The toxicity of the synthesized ILs was checked against organisms of various levels of organization: the crustacean Artemia salina; Human cell HeLa (cervical carcinoma); and bacteria with different types of cell wall, Bacillus subtilis and Escherichia coli. The toxicity was observed to depend on both the cation and anion. Choline-amino acid ILs showed a remarkable low toxicity to A. salina and HeLa cell culture, ten times less than imidazolium and pyridinium ILs. None of ionic liquids exhibited marked toxicity to bacteria, and the effect was 2-3 orders of magnitude smaller than that of the antibiotic chloramphenicol. PMID:24268343

  15. 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.

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

    PubMed Central

    Rollins, Julie B.; Conboy, John C.

    2010-01-01

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

  17. Volatilisation of ferrocene from ionic liquids: kinetics and mechanism.

    PubMed

    Fu, Chaopeng; Aldous, Leigh; Dickinson, Edmund J F; Manan, Ninie S A; Compton, Richard G

    2011-07-01

    The evaporation of dissolved ferrocene from non-volatile ionic liquids under a flow of nitrogen gas has been monitored voltammetrically and modelled mathematically. The rate of volatilisation was found to depend on the surface tension of the ionic liquid, and a model is presented. PMID:21607282

  18. 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…

  19. 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

  20. Enabling catalytic oxidation of Li2O2 at the liquid-solid interface: the evolution of an aprotic Li-O2 battery.

    PubMed

    Feng, Ningning; He, Ping; Zhou, Haoshen

    2015-02-01

    We show that by using a suitable soluble redox mediator, the charging overpotential can be reduced and the round-trip efficiency can be improved in an aprotic Li-O2 battery. Not only do we explore a new redox couple, 10-methyl-10H-phenothiazine, as a soluble catalyst that improves the electrochemical performance, but we also propose possible challenges that need to be overcome for the future improvement of aprotic Li-O2 batteries. PMID:25641874

  1. 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

  2. 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.

  3. Nonaborane and decaborane cluster anions can enhance the ignition delay in hypergolic ionic liquids and induce hypergolicity in molecular solvents.

    PubMed

    McCrary, Parker D; Barber, Patrick S; Kelley, Steven P; Rogers, Robin D

    2014-05-01

    The dissolution of nido-decaborane, B10H14, in ionic liquids that are hypergolic (fuels that spontaneously ignite upon contact with an appropriate oxidizer), 1-butyl-3-methylimidazolium dicyanamide, 1-methyl-4-amino-1,2,4-triazolium dicyanamide, and 1-allyl-3-methylimidazolium dicyanamide, led to the in situ generation of a nonaborane cluster anion, [B9H14](-), and reductions in ignition delays for the ionic liquids suggesting salts of borane anions could enhance hypergolic properties of ionic liquids. To explore these results, four salts based on [B10H13](-) and [B9H14](-), triethylammonium nido-decaborane, tetraethylammonium nido-decaborane, 1-ethyl-3-methylimidazolium arachno-nonaborane, and N-butyl-N-methyl-pyrrolidinium arachano-nonaborane were synthesized from nido-decaborane by reaction of triethylamine or tetraethylammonium hydroxide with nido-decaborane in the case of salts containing the decaborane anion or via metathesis reactions between sodium nonaborane (Na[B9H14]) and the corresponding organic chloride in the case of the salts containing the nonaborane anion. These borane cluster anion salts form stable solutions in some combustible polar aprotic solvents such as tetrahydrofuran and ethyl acetate and trigger hypergolic reactivity of these solutions. Solutions of these salts in polar protic solvents are not hypergolic. PMID:24716643

  4. Volatile times for the very first ionic liquid: understanding the vapor pressures and enthalpies of vaporization of ethylammonium nitrate.

    PubMed

    Emel'yanenko, Vladimir N; Boeck, Gisela; Verevkin, Sergey P; Ludwig, Ralf

    2014-09-01

    A hundred years ago, Paul Walden studied ethyl ammonium nitrate (EAN), which became the first widely known ionic liquid. Although EAN has been investigated extensively, some important issues still have not been addressed; they are now tackled in this communication. By combining experimental thermogravimetric analysis with time of flight mass spectrometry (TGA-ToF-MS) and transpiration method with theoretical methods, we clarify the volatilisation of EAN from ambient to elevated temperatures. It was observed that up to 419?K, EAN evaporates as contact-ion pairs leading to very low vapour pressures of a few Pascal. Starting from 419?K, the decomposition to nitric acid and ethylamine becomes more thermodynamically favourable than proton transfer. This finding was supported by DFT calculations, which provide the free energies of all possible gas-phase species, and show that neutral molecules dominate over ion pairs above 500?K, an observation that is in nearly prefect agreement with the experimental boiling point of 513?K. This result is crucial for the ongoing practical applications of protic ionic liquids such as electrolytes for batteries and fuel cells because, in contrast to high-boiling conventional solvents, EAN exhibits no significant vapour pressure below 419?K and this property fulfils the requirements for the thermal behaviour of safe electrolytes. Overall, EAN shows the same barely measurable vapour pressures as typical aprotic ionic liquids at temperatures only 70?K lower. PMID:25077820

  5. Homogeneous Liquid-Liquid Extraction of Metal Ions with a Functionalized Ionic Liquid.

    PubMed

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

    2013-05-16

    Binary mixtures of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water show an upper critical solution temperature. This solvent system has been used to extract metal ions by phase-transition extraction, using zwitterionic betaine as extractant. The system is efficient for the extraction of trivalent rare-earth, indium and gallium ions. This new type of metal extraction system avoids problems associated with the use of viscous ionic liquids, namely, the difficulty of intense mixing of the aqueous and ionic liquid phases by stirring. PMID:26282975

  6. 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).

  7. Durable Electrooptic Devices Comprising Ionic Liquids

    DOEpatents

    Burrell, Anthony K. (Los Alamos, NM); Agrawal, Anoop (Tucson, AZ); Cronin, John P. (Tucson, AZ); Tonazzi, Juan C. L. (Tucson, AZ); Warner, Benjamin P. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM)

    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.

  8. Microwave-assisted synthesis using ionic liquids.

    PubMed

    Martnez-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

  9. Metsulfuron-methyl-based herbicidal ionic liquids.

    PubMed

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

    2015-04-01

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

  10. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Burrell, Anthony K. (Los Alamos, NM); Agrawal, Anoop (Tucson, AZ); Cronin, John P. (Tucson, AZ); Tonazzi, Juan C. L. (Tucson, AZ); Warner, Benjamin P. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM)

    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.

  11. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Warner, Benjamin P. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM); Burrell, Anthony K. (Los Alamos, NM)

    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.

  12. Intermolecular vibrations and fast relaxations in supercooled ionic liquids

    NASA Astrophysics Data System (ADS)

    Ribeiro, Mauro C. C.

    2011-06-01

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

  13. 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.

  14. 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.

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

    PubMed

    Dupont, David; Renders, Evelien; Binnemans, Koen

    2016-03-17

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

  16. Morita-Baylis-Hillman reaction: ESI-MS(/MS) investigation with charge tags and ionic liquid effect origin revealed by DFT calculations.

    PubMed

    Rodrigues, Thyago S; Silva, Valter H C; Lalli, Priscila M; de Oliveira, Heibbe C B; da Silva, Wender A; Coelho, Fernando; Eberlin, Marcos N; Neto, Brenno A D

    2014-06-01

    The use of a charge-tagged acrylate derivative bearing an imidazolium tag to study the Morita-Baylis-Hillman reaction via ESI-MS(/MS) monitoring and the effect of such tag (imidazolium cations and ion pairs) over TSs is described. The ionic nature of the substrate was meant to facilitate ESI transfer to the gas phase for direct mass spectrometric analysis. The detection and characterization of charged intermediates has suggested major reaction pathways. DFT calculations considering the effect of a polar and protic solvent (methanol), of a polar and aprotic solvent (acetonitrile), and of no solvent (gas phase) were used to predict possible TSs through a common accepted intermediate. The controversial proton transfer step, which may proceed via Aggarwal's or McQuade's proposals, was evaluated. Calculations predicted the formation of electrostatic intermediate complexes with both the cation and anion when charge-tagged reagents are used. These complexes contribute to the positive ionic liquid effect, and based on the formation of these unique complexes, a rationale for the ionic liquid effect is proposed. These complexes also pointed to a plausible explanation for the positive ionic liquid effect observed in several reactions that are difficult to be carried out in organic solvents but have shown a beneficial effect when performed in ionic liquids. PMID:24815995

  17. 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.

  18. 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.

  19. 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.

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

    PubMed

    Flieger, Jolanta; Tatarczak-Michalewska, Ma?gorzata; Groszek, Anna; Blicharska, Eliza; Kocjan, Ryszard

    2015-01-01

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

  1. 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

  2. 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

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

    PubMed

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

    2008-02-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-02-01

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

  5. 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.

  6. 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.

  7. Morphology-enhanced conductivity in dry ionic liquids.

    PubMed

    Erba?, Aykut; de la Cruz, Monica Olvera

    2016-03-01

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

  8. Kinetic Charging Inversion in Ionic Liquid Electric Double Layers.

    PubMed

    Jiang, Jian; Cao, Dapeng; Jiang, De-En; Wu, Jianzhong

    2014-07-01

    The charging kinetics of electric double layers (EDLs) has a pivotal role in the performance of a wide variety of nanostructured devices. Despite the prevalent use of ionic liquids as the electrolyte, relatively little is known on the charging behavior from a microscopic perspective. Here, we study the charging kinetics of ionic liquid EDLs using a classical time-dependent density functional theory that captures the molecular excluded volume effects and electrostatic correlations. By examining variations of the ionic density profiles and the charging density in response to an electrode voltage, we find that at certain conditions, the electrode charge shows a rapid surge in its initial response, rises quickly to the maximum, and then slowly decays toward equilibrium. The electrode charge and voltage may have opposite signs when the cell width is commensurate with the layer-by-layer ionic distributions. This unusual charging behavior can be explained in terms of the oscillatory structure of ionic liquids near the electrodes. PMID:26279533

  9. Applications of Ionic Liquids as Electrolyte for Energy Devices

    NASA Astrophysics Data System (ADS)

    Yasuda, Tomohiro; Watanabe, Masayoshi

    In this paper, our studies to apply ionic liquids (ILs) as electrolyte in energy devices such as lithium ion batteries (LIB) and H2/O2 fuel cells (FC) are reviewed. Typical ionic liquids are non-volatile and thermally stable with high ionic conductivity without any molecular solvents and thus can be expected as next generation electrolyte. It is anticipated that safety of LIB can be improved by using Li+-conducting ILs and that FC can be operated under non-humidifying conditions by using H+-conducting ILs. By our studies, we could find important characteristics of ionic liquids for applying to energy devices. For LIB application, we revealed that glyme-Li salt complexes exhibit acceptable ionic conductivity with high Li+ transference number, while for PEFC application, we found that protic ILs exhibit high electrochemical activities for fuel cell reactions. The performances of LIB and non-humidifying FC using ILs were promising for the future developments.

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

    PubMed Central

    Cludio, Ana Filipa M.; Neves, Mrcia C.; Shimizu, Karina; Canongia Lopes, Jos N.; Freire, Mara G.; Coutinho, Joo 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-liquidbiomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media. PMID:26379471

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

    SciTech Connect

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

    2007-11-01

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

  12. Probing molecular interaction in ionic liquids by low frequency spectroscopy: Coulomb energy, hydrogen bonding and dispersion forces.

    PubMed

    Fumino, Koichi; Reimann, Sebastian; Ludwig, Ralf

    2014-10-28

    Ionic liquids are defined as salts composed solely of ions with melting points below 100 C. These remarkable liquids have unique and fascinating properties and offer new opportunities for science and technology. New combinations of ions provide changing physical properties and thus novel potential applications for this class of liquid materials. To a large extent, the structure and properties of ionic liquids are determined by the intermolecular interaction between anions and cations. In this perspective we show that far infrared and terahertz spectroscopy are suitable methods for studying the cation-anion interaction in these Coulomb fluids. The interpretation of the measured low frequency spectra is supported by density functional theory calculations and molecular dynamics simulations. We present results for selected aprotic and protic ionic liquids and their mixtures with molecular solvents. In particular, we focus on the strength and type of intermolecular interaction and how both parameters are influenced by the character of the ions and their combinations. We show that the total interaction between cations and anions is a result of a subtle balance between Coulomb forces, hydrogen bonds and dispersion forces. For protic ionic liquids we could measure distinct vibrational modes in the low frequency spectra indicating clearly the cation-anion interaction characterized by linear and medium to strong hydrogen bonds. Using isotopic substitution we have been able to dissect frequency shifts related to pure interaction strength between cations and anions and to different reduced masses only. In this context we also show how these different types of interaction may influence the physical properties of ionic liquids such as the melting point, viscosity or enthalpy of vaporization. Furthermore we demonstrate that low frequency spectroscopy can also be used for studying ion speciation. Low vibrational features can be assigned to contact ion pairs and solvent separated ion pairs. In conclusion we showed how detailed knowledge of the low frequency spectra can be used to understand the change in interaction strength and structure by variation of temperature, solvent polarity and solvent concentration in ionic liquids and their mixtures with molecular solvents. In principle the used combination of methods is suitable for studying intermolecular interaction in pure molecular liquids and their solutions including additive materials such as nanoparticles. PMID:24898478

  13. 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

  14. Water in Room Temperature Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Fayer, Michael

    2014-03-01

    Room temperature ionic liquids (or RTILs, salts with a melting point below 25 °C) have become a subject of intense study over the last several decades. Currently, RTIL application research includes synthesis, batteries, solar cells, crystallization, drug delivery, and optics. RTILs are often composed of an inorganic anion paired with an asymmetric organic cation which contains one or more pendant alkyl chains. The asymmetry of the cation frustrates crystallization, causing the salt's melting point to drop significantly. In general, RTILs are very hygroscopic, and therefore, it is of interest to examine the influence of water on RTIL structure and dynamics. In addition, in contrast to normal aqueous salt solutions, which crystallize at low water concentration, in an RTIL it is possible to examine isolated water molecules interacting with ions but not with other water molecules. Here, optical heterodyne-detected optical Kerr effect (OHD-OKE) measurements of orientational relaxation on a series of 1-alkyl-3-methylimidazolium tetrafluoroborate RTILs as a function of chain length and water concentration are presented. The addition of water to the longer alkyl chain RTILs causes the emergence of a long time bi-exponential orientational anisotropy decay. Such decays have not been seen previously in OHD-OKE experiments on any type of liquid and are analyzed here using a wobbling-in-a-cone model. The orientational relaxation is not hydrodynamic, with the slowest relaxation component becoming slower as the viscosity decreases for the longest chain, highest water content samples. The dynamics of isolated D2O molecules in 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) were examined using two dimensional infrared (2D IR) vibrational echo spectroscopy. Spectral diffusion and incoherent and coherent transfer of excitation between the symmetric and antisymmetric modes are examined. The coherent transfer experiments are used to address the nature of inhomogeneous broadening by observing ~ 100 fs time scale oscillations in the shape of the 2D IR spectra.

  15. Biocompatible Ionic Liquid-Derived Conducting Polymers

    NASA Astrophysics Data System (ADS)

    Firestone, Millicent; Burns, Christopher; Lee, Sungwon

    2009-03-01

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

  16. Surface modification using ionic liquid ion beams

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  17. 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

  18. 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

  19. Surfactant adsorption at the surface of mixed ionic liquids and ionic liquid water mixtures.

    PubMed

    Wakeham, Deborah; Warr, Gregory G; Atkin, Rob

    2012-09-18

    Surface tensiometry and neutron reflectivity have been used to elucidate the structure of the adsorbed layer of nonionic surfactant tetraethylene glycol tetradecyl ether (C(14)E(4)) at the free surface of the ionic liquids ethylammonium nitrate (EAN) and ethanolammonium nitrate (EtAN) and their binary mixtures with each other and with water. Surface tensions reveal that the critical micelle concentration (cmc) depends strongly on solvent composition. The adsorbed surfactant structure elucidated by neutron reflectivity shows that the level of solvation of the ethylene oxide groups varies for both the pure and mixed solvents. This is attributed to solvent-solvent interactions dominating solvent-surfactant interactions. PMID:22909055

  20. 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

  1. Radiation stability of some room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

    Radiation stability of some room temperature ionic liquids (RTILs) that find useful electrochemical applications in nuclear fuel cycle has been evaluated. The ionic liquids such as protonated betaine bis(trifluoromethylsulfonyl)imide (HbetNTf 2), aliquat 336 (tri-n-octlymethylammonium chloride), 1-butyl-3-methylimidazolium chloride (bmimCl), 1-hexyl-3-methylimidazolium chloride (hmimCl), N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyNTf 2) and N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPiNTf 2) have been irradiated to various absorbed dose levels, up to 700 kGy. The effect of gamma radiation on these ionic liquids has been evaluated by determining the variations in the physical properties such as color, density, viscosity, refractive index and electrochemical window. The changes in density, viscosity and refractive index of these ionic liquids upon irradiation were insignificant; however, the color and electrochemical window varied significantly with increase of absorbed dose.

  2. 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.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

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

    PubMed

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

    2015-01-01

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

  6. 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.

  7. 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

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

    PubMed

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

    2016-03-10

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

  9. 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.

  10. Diphosphonium Ionic Liquids as Broad Spectrum Antimicrobial Agents

    PubMed Central

    OToole, 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 ?M versus a corneal epithelial cell line or at 10 ?M 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

  11. Ionic liquids: not only structurally but also dynamically heterogeneous.

    PubMed

    Zheng, Zhuan-Ping; Fan, Wen-Hui; Roy, Soham; Mazur, Kamila; Nazet, Andreas; Buchner, Richard; Bonn, Mischa; Hunger, Johannes

    2015-01-01

    In recent years, the complex and heterogeneous structure of ionic liquids has been demonstrated; however, the consequences on the dynamics have remained elusive. Here, we use femtosecond IR spectroscopy to elucidate the local structural dynamics in protic alkylammonium-based ionic liquids. The structural relaxation after an ultrafast temperature increase, following vibrational excitation and subsequent relaxation of the N-D (or N-H) stretching vibration, is found to vary substantially between the ionic and hydrophobic subdomains. The dynamics in the ionic domains are virtually unaffected by the alkyl chain length and is, therefore, decoupled from viscosity. Equilibration within the hydrophobic subdomains, as evident from the dynamics of the C-H stretching vibration, is faster than that in the ionic domains and shows a remarkably low thermal activation. PMID:25411079

  12. 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.

  13. 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

  14. 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.

  15. Slightly viscous amino acid ionic liquids: synthesis, properties, and calculations.

    PubMed

    He, Ling; Tao, Guo-Hong; Parrish, Damon A; Shreeve, Jean'ne M

    2009-11-19

    Slightly viscous N-alkyl-substituted glycine ester ionic liquids were prepared via alkylation of glycine ethyl esters with appropriate haloalkanes followed by anion exchange with lithium bis(trifluoromethanesulfonyl)amide. These ionic liquids have been characterized by IR, NMR, elemental analysis, thermal stability, phase behavior, viscosity, and density. Compound 9 crystallizes in the monoclinic system, P2(1)/c. The viscosities of the N,N,N-trialkyl-substituted glycine ester ionic liquids (6, 8, 10) are in the approximately 200 to 400 cP range at 25 degrees C. While exhibiting liquid characteristics analogous to the traditional heterocyclic ionic liquids, these new liquids are much less viscous than known amino acid ionic liquids. The correlation of viscosity and temperature was determined. To understand the influence of the alkyl and ester-substituted groups on viscosity, the electronic distributions and the electrostatic potential surfaces of the glycine-based cations, including glycine (Gly(+)), glycine ethyl ester (GlyET(+)), N,N-dimethyl glycine (DMGly(+)), N,N-dimethyl glycine ethyl ester (DMGlyET(+)), N,N-dimethyl-N-propyl glycine ethyl ester (DMPGlyET(+)), N,N-dimethyl-N-3-fluoropropyl glycine ethyl ester (DMPFGlyET(+)), and N-butyl-N,N-dimethyl glycine ethyl ester (DMBGlyET(+)) cations have been investigated and analyzed. The possible effects on the viscosity coming from the intermolecular interactions arising from Coulomb interactions, hydrogen bonding, polarizability effects, and van der Waals interactions are considered. PMID:19856931

  16. 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

  17. Interaction of nonionic surfactants and hydrophilic ionic liquids in aqueous solutions: can short ionic liquids be more than a solvent?

    PubMed

    Comelles, Francesc; Ribosa, Isabel; Gonzlez, Juan Jos; Garcia, Maria Teresa

    2012-10-16

    The interaction between an ethoxylated nonionic surfactant (C(12-14)EO(8)) and three conventional hydrophilic imidazolium-based ionic liquids (bmim-octyl SO(4), bmim-methyl SO(4), and bmim-BF(4)) in aqueous solution has been investigated. In most of the reported studies where a surfactant is dissolved in an ionic liquid aqueous solution, conventional ionic liquids are merely considered to be solvents. Consequently, the resulting critical micelle concentration (cmc) is considered to be that of the surfactant. However, given that the three ionic liquids selected showed the typical shape of a surface-active compound when the surface tension was plotted against concentration, the role of these compounds as secondary surfactants and consequently the possibility of mixed-micelle formation have been investigated. Different series of experiments where a surfactant and an ionic liquid were combined in a wide range of mole ratios have been performed and treated as typical binary surfactant systems in aqueous solution. It has been found for the three surfactant/ionic liquid systems that depending on the surfactant mole fraction, ?(1), attractive or repulsive interactions in mixed-micelle formation are produced. Therefore, when we select the appropriate ?(1) these systems can be adjusted to a given application, depending on whether monomers or micelles are mainly required. PMID:22998152

  18. 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.

  19. Carbon Dioxide Separation with Supported Ionic Liquid Membranes

    SciTech Connect

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

    2007-05-01

    A practical form of CO2 capture at water-gas shift conditions in the IGCC process could serve the dual function of producing a pure CO2 stream for sequestration and forcing the equilibrium-limited shift reaction to completion enriching the stream in H2. The shift temperatures, ranging from the low temperature shift condition of 260C to the gasification condition of 900C, limit capture options by diminishing associative interactions which favor removal of CO2 from the gas stream. Certain sorption interactions, such as carbonate formation, remain available but generally involve exceptionally high sorbent regeneration energies that contribute heavily to parasitic power losses. Carbon dioxide selective membranes need only establish an equilibrium between the gas phase and sorption states in order to transport CO2, giving them a potential energetic advantage over other technologies. Supported liquid membranes take advantage of high, liquid phase diffusivities and a solution diffusion mechanism similar to that observed in polymeric membranes to achieve superior permeabilities and selectivites. 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 CO2 solubility relative to light gases such as H2, are excellent candidates 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 ionic liquids including 1-hexyl-3-methyl-imidazolium bis(trifuoromethylsulfonyl)imide 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 the resulting materials for membrane performance. Improvements to the ionic liquid and support have allowed testing of these supported ionic liquid membranes at temperatures up to 300C without loss of support mechanical stability or degradation of the ionic liquid. Substantial improvements in selectivity have also been observed at elevated temperature with the best membrane currently achieving optimum performance at 75C.

  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. Molecular dynamics simulations of the surface tension of ionic liquids

    NASA Astrophysics Data System (ADS)

    Gonzlez-Melchor, Minerva; Bresme, Fernando; Alejandre, Jos

    2005-03-01

    We report molecular dynamics computer simulations of the surface tension and interfacial thickness of ionic liquid-vapor interfaces modeled with a soft core primitive model potential. We find that the surface tension shows an anomalous oscillatory behavior with interfacial area. This observation is discussed in terms of finite size effects introduced by the periodic boundary conditions employed in computer simulations. Otherwise we show that the thickness of the liquid-vapor interface increases with surface area as predicted by the capillary wave theory. Data on the surface tension of size-asymmetric ionic liquids are reported and compared with experimental data of molten salts. Our data suggest that the surface tensions of size-asymmetric ionic liquids do not follow a corresponding states law.

  2. Photon-Upconverting Ionic Liquids: Effective Triplet Energy Migration in Contiguous Ionic Chromophore Arrays.

    PubMed

    Hisamitsu, Shota; Yanai, Nobuhiro; Kimizuka, Nobuo

    2015-09-21

    Inspired by the bicontinuous ionic-network structure of ionic liquids (ILs), we developed a new family of photofunctional ILs which show efficient triplet energy migration among contiguously arrayed ionic chromophores. A novel fluorescent IL, comprising an aromatic 9,10-diphenylanthracene 2-sulfonate anion and an alkylated phosphonium cation, showed pronounced interactions between chromophores, as revealed by its spectral properties. Upon dissolving a triplet sensitizer, the IL demonstrated photon upconversion based on triplet-triplet annihilation (TTA-UC). Interestingly, the TTA-UC process in the chromophoric IL was optimized at a much lower excitation intensity compared to the previous nonionic liquid TTA-UC system. The superior TTA-UC in this IL system is characterized by a relatively high triplet diffusion constant (1.6310(-6)?cm(2)?s(-1)) which is ascribed to the presence of ionic chromophore networks in the IL. PMID:26288261

  3. 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

  4. Structure-morphology-property relationships in polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Sangoro, Joshua; Heres, Maximilian; Minutolo, Joseph; Shamblin, Jacob; Lang, Maik; Berdzinski, Stefan; Strehmel, Veronika; Paddison, Stephen

    2015-03-01

    Charge transport and structural dynamics in systematic series of polymerized ammonium- and imidazolium- based ionic liquids are investigated by broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, and x-ray as well neutron scattering techniques. Detailed analysis reveal strong decoupling of these processes in the polymerized ionic liquids, implying failure of the classical theories in describing charge transport and molecular dynamics in these systems. In addition, a strong correlation is observed between the ionic conductivity at the respective calorimetric glass transition temperatures and the morphologies revealed by the scattering experiments. In this talk, a physical explanation of the origin of the observed decoupling of ionic conductivity from structural dynamics will be proposed.

  5. Effect of liquid properties on electrosprays from externally wetted ionic liquid ion sources

    NASA Astrophysics Data System (ADS)

    Castro, S.; Larriba, C.; Fernandez de la Mora, J.; Lozano, P.; Smer, S.; Yoshida, Y.; Saito, G.

    2007-11-01

    Ionic liquid ion sources (ILISs) are externally wetted and electrochemically etched and sharpened tungsten tips used as electrospraying sources for ionic liquids in a vacuum. They have recently shown an ability to operate as emitters of pure ion beams (no drops), even with ionic liquids of moderate surface tension (?<40dyn/cm) and electrical conductivity (K<1S/m) that had in all prior reports (all based on conventional internally fed capillary tips) always operated in the mixed ion-drop regime. The present study uses time of flight mass spectrometry to analyze full ion beams emitted from ILISs for a diversity of ionic liquids with properties in the wide range 0.26liquids tested achieve the purely ionic regime. The main effect of reducing electrical conductivity is a reduction of the emission current from 180to10nA.

  6. Do solvation layers of ionic liquids influence electrochemical reactions?

    PubMed

    Endres, Frank; Hfft, Oliver; Borisenko, Natalia; Gasparotto, Luiz Henrique; Prowald, Alexandra; Al-Salman, Rihab; Carstens, Timo; Atkin, Rob; Bund, Andreas; Zein El Abedin, Sherif

    2010-02-28

    In this discussion paper we discuss our recent results on the electrodeposition of materials and in situ STM/AFM measurements which demonstrate that ionic liquids should not be regarded as neutral solvents which all have similar properties. In particular, we focus on differences in interfacial structure (solvation layers) on metal electrodes as a function of ionic liquid species. Recent theoretical and experimental results show that conventional double layers do not form on metal electrodes in ionic liquid systems. Rather, a multilayer architecture is present, with the number of layers determined by the ionic liquid species and the properties of the surface; up to seven discrete interfacial solvent layers are present on electrode surfaces, consequently there is no simple electrochemical double layer. Both the electrodeposition of aluminium and of tantalum are strongly influenced by ionic liquids: in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]TFSA, aluminium is obtained as a nanomaterial, whereas in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]TFSA, a microcrystalline material is made. Tantalum can be deposited from [Py(1,4)]TFSA, whereas from [EMIm]TFSA only non-stoichiometric tantalum fluorides TaF(x) are obtained. It is likely that solvation layers influence these reactions. PMID:20145836

  7. 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

  8. 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

  9. 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.

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

    PubMed

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

    2016-01-01

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

  11. 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.

  12. 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.

  13. 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.

  14. 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 supercooled state and analysis using schematic mode coupling theory (MCT) show that RTILs have bulk liquid orientational relaxation dynamics that are indistinguishable in their nature from common nonpolar organic liquids that supercool. This behavior of the RTILs occurs in spite of the segregation into ionic and organic regions. However, when small amounts of water are added to RTILs at room temperature, novel dynamics are observed for the RTILs with long alkyl chains that have not been observed in OHD-OKE experiments on organic liquids. The results are interpreted as water induced structure in the ionic regions that causes the long alkyl chains to organize and 'lock up.' The dynamical measurements indicate that this lock up is involved in the formation of RTIL gels that occur over a narrow range of water concentrations.

  15. Thermophysical properties of phosphonium-based ionic liquids

    PubMed Central

    Bhattacharjee, Arijit; Lopes-da-Silva, Jos A.; Freire, Mara G.; Coutinho, Joo 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

  16. 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).

  17. Determination of sulfonamides in butter samples by ionic liquid magnetic bar liquid-phase microextraction high-performance liquid chromatography.

    PubMed

    Wu, Lijie; Song, Ying; Hu, Mingzhu; Xu, Xu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

    2015-01-01

    A novel, simple, and environmentally friendly pretreatment method, ionic liquid magnetic bar liquid-phase microextraction, was developed for the determination of sulfonamides in butter samples by high-performance liquid chromatography. The ionic liquid magnetic bar was prepared by inserting a stainless steel wire into the hollow of a hollow fiber and immobilizing ionic liquid in the micropores of the hollow fiber. In the extraction process, the ionic liquid magnetic bars were used to stir the mixture of sample and extraction solvent and enrich the sulfonamides in the mixture. After extraction, the analyte-adsorbed ionic liquid magnetic bars were readily isolated with a magnet from the extraction system. It is notable that the present method was environmentally friendly since water and only several microliters of ionic liquid were used in the whole extraction process. Several parameters affecting the extraction efficiency were investigated and optimized, including the type of ionic liquid, sample-to-extraction solvent ratio, the number of ionic liquid magnetic bars, extraction temperature, extraction time, salt concentration, stirring speed, pH of the extraction solvent, and desorption conditions. The recoveries were in the range of 73.25-103.85% and the relative standard deviations were lower than 6.84%. The experiment results indicated that the present method was effective for the extraction of sulfonamides in high-fat content samples. PMID:25384336

  18. Energy Efficient Electrochromic Windows Incorporating Ionic Liquids

    SciTech Connect

    Cheri Boykin; James Finley; Donald Anthony; Julianna Knowles; Richard Markovic; Michael Buchanan; Mary Ann Fuhry; Lisa Perrine

    2008-11-30

    One approach to increasing the energy efficiency of windows is to control the amount of solar radiation transmitted through a window by using electrochromic technology. What is unique about this project is that the electrochromic is based on the reduction/oxidation reactions of cathodic and anodic organic semi-conducting polymers using room temperature ionic liquids as ion transport electrolytes. It is believed that these types of coatings would be a lower cost alternative to traditional all inorganic thin film based electrochromic technologies. Although there are patents1 based on the proposed technology, it has never been reduced to practice and thoroughly evaluated (i.e. durability and performance) in a window application. We demonstrate that by using organic semi-conductive polymers, specific bands of the solar spectrum (specifically visible and near infrared) can be targeted for electrochemical variable transmittance responsiveness. In addition, when the technology is incorporated into an insulating glass unit, the energy parameters such as the solar heat gain coefficient and the light to solar gain ratio are improved over that of a typical insulating glass unit comprised of glass with a low emissivity coating. A minimum of {approx}0.02 quads of energy savings per year with a reduction of carbon emissions for electricity of {approx}320 MKg/yr benefit is achieved over that of a typical insulating glass unit including a double silver low-E coating. Note that these values include a penalty in the heating season. If this penalty is removed (i.e. in southern climates or commercial structures where cooling is predominate year-round) a maximum energy savings of {approx}0.05 quad per year and {approx}801 MKg/yr can be achieved over that of a typical insulating glass unit including a double silver low-E coating. In its current state, the technology is not durable enough for an exterior window application. The primary downfall is that the redox chemistry fails to recover to a bleached state upon exposure to heat and solar radiation while being cycled over time from the bleached to the dark state. Most likely the polymers are undergoing degradation reactions which are accelerated by heat and solar exposure while in either the reduced or oxidized states and the performance of the polymers is greatly reduced over time. For this technology to succeed in an exterior window application, there needs to be more work done to understand the degradation of the polymers under real-life application conditions such as elevated temperatures and solar exposure so that recommendations for improvements in to the overall system can be made. This will be the key to utilizing this type of technology in any future real-life applications.

  19. Hydrolysis and Partial Recycling of a Chloroaluminate Ionic Liquid

    PubMed Central

    Fang, Ming-Hong; Wang, Li-Sheng

    2007-01-01

    Hydrolysis of the ionic liquid Et3NHCl-2AlCl3 and a process for recycling the triethylamine were studied. When the hydrolysis was carried out at a relatively high temperature, the released HCl could be absorbed more easily. With addition of sodium hydroxide to the aqueous hydrolysis solution, a feasible process for recycling triethylamine was developed, involving first distillation of triethylamine, followed by filtration of the aluminium hydroxide. The yield of recovered triethylamine was about 95%. The triethylhydrogenammonium chloride prepared from the recycled triethylamine was of good purity and could be reused to synthesize new chloroaluminate ionic liquids.

  20. Capturing CO2: conventional versus ionic-liquid based technologies

    NASA Astrophysics Data System (ADS)

    Privalova, E. I.; Mäki-Arvela, P.; Murzin, Dmitry Yu; Mikkhola, J. P.

    2012-05-01

    Since CO2 facilitates pipeline corrosion and contributes to a decrease of the calorific value of gaseous fuels, its removal has become an issue of significant economic importance. The present review discusses various types of traditional CO2 capture technologies in terms of their efficiency, complexity in system design, costs and environmental impact. The focus is hereby not only on conventional approaches but also on emerging "green" solvents such as ionic liquids. The suitability of different ionic liquids as gas separation solvents is discussed in the present review and a description on their synthesis and properties in terms of CO2 capture is provided. The bibliography includes 136 references.

  1. 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

  2. Lithium solvation in bis(trifluoromethanesulfonyl)imide-based ionic liquids.

    PubMed

    Lassgues, Jean-Claude; Grondin, Joseph; Talaga, David

    2006-12-28

    The lithium solvation in (1 -x)(EMI-TFSI), xLiTFSI ionic liquids where EMI(+) is the 1-ethyl-3-methylimidazolium cation and TFSI(-) the bis(trifluoromethanesulfonyl)imide anion, is shown by Raman spectroscopy to involve essentially [Li(TFSI)(2)](-) anionic clusters for 0 < x < 0.4, but addition of stoichiometric amounts of solvents S such as oligoethers changes the lithium solvation into [Li(S)(m)](+) cationic clusters; the lithium transference number in TFSI-based ionic liquid electrolytes for lithium batteries should thus be strongly improved. PMID:17149483

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

    SciTech Connect

    Dr. Ramana Reddy

    2009-01-31

    EXECUTIVE SUMMARY The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30C was found to be quasi-reversible, with the charge transfer coefficient ? = 0.40. Nucleation phenomena involved in aluminum deposition on copper in AlCl3-BMIMCl electrolyte was found to be instantaneous followed by diffusion controlled three-dimensional growth of nuclei. Diffusion coefficient (Do) of the electroactive species Al2Cl7 ion was in the range from 6.5 to 3.9107 cm2?s1 at a temperature of 30C. Relatively little research efforts have been made toward the fundamental understanding and modeling of the species transport and transformation information involved in ionic liquid mixtures, which eventually could lead to quantification of electrochemical properties. Except that experimental work in this aspect usually is time consuming and expensive, certain characteristics of ionic liquids also made barriers for such analyses. Low vapor pressure and high viscosity make them not suitable for atomic absorption spectroscopic measurement. In addition, aluminum electrodeposition in ionic liquid electrolytes are considered to be governed by multi-component mass, heat and charge transport in laminar and turbulent flows that are often multi-phase due to the gas evolution at the electrodes. The kinetics of the electrochemical reactions is in general complex. Furthermore, the mass transfer boundary layer is about one order of magnitude smaller than the thermal and hydrodynamic boundary layer (ReL?10,000). Other phenomena that frequently occur are side reactions and temperature or concentration driven natural convection. As a result of this complexity, quantitative knowledge of the local parameters (current densities, ion concentrations, electrical potential, temperature, etc.) is very difficult to obtain. This situation is a serious obstacle for improving the quality of products, efficiency of manufacturing and energy consumption. The gap between laboratory/batch scale processing with global process control and nanoscale deposit surface and materials specifications needs to be bridged. A breakthrough can only be realized if on each scale the occurring phenomena are understood and quantified. Multiscale numerical modelin

  4. 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.

  5. 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

  6. Origins of Symmetry in Polymer Ionic Liquid Phase Diagrams

    NASA Astrophysics Data System (ADS)

    Lipson, Jane; White, Ronald

    2013-03-01

    Recent experimental work [Lee et al. Macromolecules 45, 3627 (2012)] reveals rather symmetric looking coexistence curves for poly(ethylene oxide) in [EMIM][BF4]. This is in marked contrast to solutions involving non-ionic solvents, which show a characteristic and strong asymmetry, correlated with the molecular weight disparity between the two components. Using our simple theoretical approach we show that the special character of this systems derives from two thermodynamically-based properties. First, we find that the ionic solvent has a considerably stronger cohesive energy densities than non-ionic counterparts. In addition, we propose that aggregation in the ionic liquid has a significant impact on the entropy of mixing, typically a strong driving force for miscibility in polymer solutions. In this talk we explain how each of these features serves to drive the critical composition to the middle of the phase diagram. Financial support from the National Science Foundation (DMR-1104658) is gratefully acknowledged.

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

    DOEpatents

    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.

  8. Dynamic wetting of a fluoropolymer surface by ionic liquids.

    PubMed

    Li, Hua; Sedev, Rossen; Ralston, John

    2011-03-01

    The spontaneous spreading of ionic liquids on a fluoropolymer surface (Teflon AF1600) in air is investigated by high-speed video microscopy. Six ionic liquids (EMIM BF(4), BMIM BF(4), OMIM BF(4), EMIM NTf(2), BMIM NTf(2) and HMIM NTf(2)) are used as probe liquids. The dependence of the dynamic contact angle on contact line velocity is interpreted with a hydrodynamic model and a molecular-kinetic model. The usefulness of the hydrodynamic model is rather limited. There is a good correspondence between the molecular dimensions of the liquids and the physical parameters of the molecular-kinetic model. The viscous and molecular-kinetic contributions to energy dissipation are calculated, revealing that energy is dissipated in the bulk as well as at the contact line during dynamic wetting. There are wide ramifications of these results in areas ranging from lubrication and biology to minerals processing and petroleum recovery. PMID:21240433

  9. Formation of Interconnected Aggregates in Aqueous Dicationic Ionic Liquid Solutions.

    PubMed

    Bhargava, B L; Klein, Michael L

    2010-03-01

    The structure and organization in an aqueous solution of a gemini surfactant, the dicationic ionic liquid 1,3-bis(3-decylimidazolium-1-yl) propane bromide, and its vapor-liquid interface have been studied using molecular dynamics simulations at room temperature. Starting from a uniform distribution of cations, the system is found to spontaneously evolve forming cross-linked cationic micellar aggregates. Alkyl tails are typically found buried inside the aggregates to minimize their unfavorable interactions with water, whereas the polar head groups are present at the micellar surfaces, exposed to water. Anions are found throughout the solution and are not strongly bound to the cations. Cationic micellar aggregates exhibit an interesting behavior: interconnection mediated by head groups, a phenomenon which is not observed in monocationic ionic liquid solutions. The structure of the vapor-liquid interface of the solution, the structure of the micellar aggregates, and the distribution of counterions are also discussed. PMID:26613314

  10. 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

  11. 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

  12. 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...

  13. High performance batteries with carbon nanomaterials and ionic liquids

    SciTech Connect

    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.

  14. 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...

  15. 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.

  16. Are Room-Temperature Ionic Liquids Dilute Electrolytes?

    PubMed

    Lee, Alpha A; Vella, Dominic; Perkin, Susan; Goriely, Alain

    2015-01-01

    An important question in understanding the structure of ionic liquids is whether ions are truly "free" and mobile, which would correspond to a concentrated ionic melt, or are rather "bound" in ion pairs, that is, a liquid of ion pairs with a small concentration of free ions. Recent surface force balance experiments from different groups have given conflicting answers to this question. We propose a simple model for the thermodynamics and kinetics of ion pairing in ionic liquids. Our model takes into account screened ion-ion, dipole-dipole, and dipole-ion interactions in the mean-field limit. The results of this model suggest that almost two-thirds of the ions are free at any instant, and ion pairs have a short lifetime comparable to the characteristic time scale for diffusion. These results suggest that there is no particular thermodynamic or kinetic preference for ions to reside in pairs. We therefore conclude that ionic liquids are concentrated, rather than dilute, electrolytes. PMID:26263105

  17. 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...

  18. Growth of sputter-deposited gold nanoparticles in ionic liquids.

    PubMed

    Vanecht, Evert; Binnemans, Koen; Seo, Jin Won; Stappers, Linda; Fransaer, Jan

    2011-08-14

    The growth of gold nanoparticles (NPs) synthesized by sputter deposition on an ionic liquid surface is studied in situ in the bulk phase of the ionic liquids (ILs) 1-butyl-3-methylimidazolium dicyanamide [C(1)C(4)Im][N(CN)(2)], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [C(1)C(4)Im][Tf(2)N], 1-butyl-3-methylimidazolium tetrafluoroborate [C(1)C(4)Im][BF(4)], 1-butyl-3-methylimidazolium hexafluorophosphate [C(1)C(4)Im][PF(6)] and 1-butyl-3-methylimidazolium triflate [C(1)C(4)Im][TfO]. It is found that primary nanoparticles with a diameter smaller than 2.5 nm are present in the sample immediately after sputtering. Growth of these primary particles proceeds after the end of the sputtering process and stops when the nanoparticles reach a certain size. Depending on the viscosity of the ionic liquid this growth process can proceed several hours to several days. The growth speed is fastest for the least viscous ionic liquid and follows the trend [C(1)C(4)Im][N(CN)(2)] > [C(1)C(4)Im][Tf(2)N] > [C(1)C(4)Im][TfO] > [C(1)C(4)Im][BF(4)] > [C(1)C(4)Im][PF(6)]. It is also found that a higher concentration of sputtered gold results in faster growth of the gold nanoparticles. A discussion on the growth mechanism of sputtered gold NPs is included. PMID:21674115

  19. Highly ion-conducting poly(ionic liquid) layers.

    PubMed

    Wood, Thomas J; Schofield, Wayne C E; Lund, Peter; Larsen, Mikkel J; Badyal, Jas Pal S

    2012-10-21

    Highly ion-conducting poly(ionic liquid) thin films have been prepared in the absence of solvents utilizing a simple 2-step approach comprising pulsed plasmachemical deposition of 1-allylimidazole followed by vapour-phase quaternization with 1-bromobutane. PMID:22962661

  20. 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

  1. 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.

  2. Unexpected Preferential Dehydration of Artemisinin in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Sanders, Marc W.; Wright, Lawrence; Tate, Lauren; Fairless, Gayle; Crowhurst, Lorna; Bruce, Neil C.; Walker, Adam J.; Hembury, Guy A.; Shimizu, Seishi

    2009-09-01

    Thermodynamic measurements (at 298 K) reveal that a crucial step in the extraction process of the key antimalarial drug artemisinin by ionic liquids (ILs), namely, precipitation through the addition of water, is driven by artemisinin dehydration due to the differences in the water's interaction with the bulk ILs, rather than with the artemisinin itself.

  3. 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.

  4. 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,...

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

    DOEpatents

    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.

  6. 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.

  7. 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

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

    PubMed

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

    2014-01-01

    Lab-on-a-chip and miniaturized systems have gained significant popularity motivated by marked differences in material performance at the micro-to-nano-scale realm. However, to fully exploit micro-to-nano-scale chemistry, solvent volatility and lack of reproducibility need to be overcome. Here, we combine the non-volatile and versatile nature of ionic liquids with microcontact printing in an attempt to establish a facile protocol for high throughput fabrication of open microreactors and microfluidics. The micropatterned ionic liquid droplets have been demonstrated as electrochemical cells and reactors for microfabrication of metals and charge transfer complexes, substrates for immobilization of proteins and as membrane-free high-performance amperometric gas sensor arrays. The results suggest that miniaturized ionic liquid systems can be used to solve the problems of solvent volatility and slow mass transport in viscous ionic liquids in lab-on-a-chip devices, thus providing a versatile platform for a diverse number of applications. PMID:24781644

  9. 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.

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

    PubMed

    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

  11. Fission-Product Separation Based on Room-Temperature Ionic Liquids

    SciTech Connect

    Luo, Huimin; Hussey, Charles L.

    2005-09-30

    The objectives of this project are (a) to synthesize new ionic liquids tailored for the extractive separation of Cs + and Sr 2+; (b) to select optimum macrocyclic extractants through studies of complexation of fission products with macrocyclic extractants and transport in new extraction systems based on ionic liquids; (c) to develop efficient processes to recycle ionic liquids and crown ethers; and (d) to investigate chemical stabilities of ionic liquids under strong acid, strong base, and high-level-radiation conditions.

  12. Fission-Product Separation Based on Room-Temperature Ionic Liquids

    SciTech Connect

    Luo, Huimin

    2006-11-15

    The objectives of this project are (a) to synthesize new ionic liquids tailored for the extractive separation of Cs + and Sr 2+; (b) to select optimum macrocyclic extractants through studies of complexation of fission products with macrocyclic extractants and transport in new extraction systems based on ionic liquids; (c) to develop efficient processes to recycle ionic liquids and crown ethers; and (d) to investigate chemical stabilities of ionic liquids under strong acid, strong base, and high-level-radiation conditions.

  13. 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.

  14. Electrolytic Conductivity of Four Imidazolium-Based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Calado, Marta S.; Diogo, Joo C. F.; Correia da Mata, Jos L.; Caetano, Fernando J. P.; Visak, Zoran P.; Fareleira, Joo 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.

  15. On the electrodeposition of titanium in ionic liquids.

    PubMed

    Endres, F; Zein El Abedin, S; Saad, A Y; Moustafa, E M; Borissenko, N; Price, W E; Wallace, G G; MacFarlane, D R; Newman, P J; Bund, A

    2008-04-28

    The ability to electrodeposit titanium at low temperatures would be an important breakthrough for making corrosion resistant layers on a variety of technically important materials. Ionic liquids have often been considered as suitable solvents for the electrodeposition of titanium. In the present paper we have extensively investigated whether titanium can be electrodeposited from its halides (TiCl(4), TiF(4), TiI(4)) in different ionic liquids, namely1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm]Tf(2)N), 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)amide ([BMP]Tf(2)N), and trihexyltetradecyl-phosphonium bis(trifluoromethylsulfonyl)amide ([P(14,6,6,6)]Tf(2)N). Cyclic voltammetry and EQCM measurements show that, instead of elemental Ti, only non-stoichiometric halides are formed, for example with average stoichiometries of TiCl(0.2), TiCl(0.5) and TiCl(1.1). In situ STM measurements show that-in the best case-an ultrathin layer of Ti or TiCl(x) with thickness below 1 nm can be obtained. In addition, results from both electrochemical and chemical reduction experiments of TiCl(4) in a number of these ionic liquids support the formation of insoluble titanium cation-chloride complex species often involving the solvent. Solubility studies suggest that TiCl(3) and, particularly, TiCl(2) have very limited solubility in these Tf(2)N based ionic liquids. Therefore it does not appear possible to reduce Ti(4+) completely to the metal in the presence of chloride. Successful deposition processing for titanium in ionic liquids will require different maybe tailor-made titanium precursors that avoid these problems. PMID:18404225

  16. 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.

  17. Reaction kinetics of CO2 absorption in to phosphonium based anion-functionalized ionic liquids.

    PubMed

    Gurkan, Burcu E; Gohndrone, Thomas R; McCready, Mark J; Brennecke, Joan F

    2013-05-28

    The reaction kinetics between CO2 and trihexyl(tetradecyl)phosphonium ([P66614])-based ionic liquids (ILs) with prolinate ([Pro]), 2-cyanopyrrolide ([2-CNpyr]), and 3-(trifluoromethyl)pyrazolide ([3-CF3pyra]) anions are studied at temperatures from 22-60 °C. The absorption of CO2 is carried out in a stirred reactor under pseudo first order conditions. ILs are diluted to concentrations of 0.05, 0.1 and 0.15 M with tetraglyme--a nonreactive, low volatility solvent with much lower viscosity than the ILs. Physical solubility of CO2 in the mixtures is calculated using correlations developed from CO2 solubility measurements in tetraglyme and the N2O-analogy for ILs and dilute IL solutions. The diffusivity of CO2 is estimated from viscosity-dependent correlations chosen after a thorough literature review. The results indicate partial first order reaction kinetics with respect to IL with values ranging from 19,500 L mol(-1) s(-1) ([P66614][Pro]) to 3200 L mol(-1) s(-1) ([P66614][3-CF3pyra]) at 22 °C. The second order reaction rate constants follow Arrhenius behavior with the highest activation energy of 43 kJ mol(-1) measured for [P66614][Pro]. ILs with aprotic heterocylic anions (AHA), on the other hand, show small activation energies of 18 and 11 kJ mol(-1) for [P66614][3-CF3pyra] and [P66614][2-CNpyr], respectively. The ILs studied in this work exhibit reactivity comparable to or higher than common aqueous amines. High reaction rates and tunable capacity make ILs, and AHA ILs in particular, attractive solvents for CO2 separations. PMID:23598368

  18. 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.

  19. 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...

  20. 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

  1. A polymerized ionic liquid-supported B12 catalyst with a ruthenium trisbipyridine photosensitizer for photocatalytic dechlorination in ionic liquids.

    PubMed

    Zhang, Wei; Shimakoshi, Hisashi; Houfuku, Noriyuki; Song, Xi-Ming; Hisaeda, Yoshio

    2014-10-01

    By immobilizing a B12 complex and a Ru(ii) trisbipyridine photosensitizer in a polymerized ionic liquid (PIL), a visible light-driven photocatalyst was developed. The synthesized copolymer was characterized by GPC and DLS, and using UV-vis absorption spectra and luminescence spectra. The Ru(ii) trisbipyridine photosensitizer in the copolymer showed an enhanced emission compared to that of the monomer in the ionic liquid, 1-butyl-4-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C4mim][NTf2]). Formation of the Co(i) species of the B12 complex in the copolymer was confirmed by the UV-vis spectral change in [C4mim][NTf2] containing a sacrificial reductant (triethanolamine) under irradiation with visible light. The copolymer showed a high photocatalytic activity in various ionic liquids for 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) dechlorination with ?99% conversion after visible light irradiation for 2 h. Furthermore, both the B12 catalyst and photosensitizer in the polymer were easily recycled for use with the ionic liquid solvent without any loss of catalytic activity. PMID:25118045

  2. Static and dynamic wetting behaviour of ionic liquids.

    PubMed

    Delcheva, Iliana; Ralston, John; Beattie, David A; Krasowska, Marta

    2015-08-01

    Ionic liquids (ILs) are a unique family of molecular liquids ('molten salts') that consist of a combination of bulky organic cations coupled to inorganic or organic anions. The net result of steric hindrance and strong hydrogen bonding between components results in a material that is liquid at room temperature. One can alter the properties of ionic liquids through chemical modification of anion and cation, thus tailoring the IL for a given application. One such property that can be controlled or selected is the wettability of an IL on a particular solid substrate. However, the study of wetting of ionic liquids is complicated by the care required for accurate and reproducible measurement, due to both the susceptibility of the IL properties to water content, as well as to the sensitivity of wettability measurements to the state of the solid surface. This review deals with wetting studies of ILs to date, including both static and dynamic wetting, as well as issues concerning line tension and the formation of precursor and wetting films. PMID:25103860

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

    PubMed

    Hoth, Judith; Hausen, Florian; Mser, 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

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

    NASA Astrophysics Data System (ADS)

    Hoth, Judith; Hausen, Florian; Mser, 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.

  5. Nanoscale organization in aqueous dicationic ionic liquid solutions.

    PubMed

    Bhargava, B L; Klein, Michael L

    2011-09-01

    Coarse-grained molecular dynamics simulations have been performed on aqueous solutions of the gemini dicationic ionic liquid 1,5-bis(3-decylimidazolium-1-yl) pentane bromide at room temperature to study the structure and organization in the solution. Several trajectories corresponding to different concentrations of the ionic liquid (IL) in the solution were generated for about a microsecond. The 40% (w/w) aqueous mixture evolves to a hexagonal structure starting from a random distribution of ions. Spontaneous aggregation of cations was observed in solutions at lower concentrations. Unlike the monocationic ILs, which form spherical aggregates, the aggregates observed in the dicationic IL solution displayed a near-hexagonal arrangement of the hydrophobic cores that were connected to each other by hydrophilic head groups. Anions were found to be present close to the polar head groups. The formation of the interlinked aggregates from a random distribution and the organization at the vapor-liquid interface are also discussed. PMID:21797249

  6. 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

  7. Recent progress on dielectric properties of protic ionic liquids

    NASA Astrophysics Data System (ADS)

    Wojnarowska, Zaneta; Paluch, Marian

    2015-02-01

    Protic ionic liquids (PILs) are key materials for a wide range of emerging technologies. In particular, these systems have long been envisioned as promising candidates for fuel cells. Therefore, in recent years special attention has been devoted to thorough studies of these compounds. Amongst others, dielectric properties of PILs at ambient and elevated pressure have become the subject of intense research. The reason for this lies in the role of broadband dielectric spectroscopy in recognizing the conductivity mechanism in protic ionic systems. In this paper, we summarize the dielectric results of various PILs reflecting recent advances in this field.

  8. Recent progress on dielectric properties of protic ionic liquids.

    PubMed

    Wojnarowska, Zaneta; Paluch, Marian

    2015-02-25

    Protic ionic liquids (PILs) are key materials for a wide range of emerging technologies. In particular, these systems have long been envisioned as promising candidates for fuel cells. Therefore, in recent years special attention has been devoted to thorough studies of these compounds. Amongst others, dielectric properties of PILs at ambient and elevated pressure have become the subject of intense research. The reason for this lies in the role of broadband dielectric spectroscopy in recognizing the conductivity mechanism in protic ionic systems. In this paper, we summarize the dielectric results of various PILs reflecting recent advances in this field. PMID:25634823

  9. Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Zeller, Robert August

    Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm + cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.

  10. Bulk and liquid-vapor interface of pyrrolidinium-based ionic liquids: a molecular simulation study.

    PubMed

    Paredes, Xavier; Fernndez, Josefa; Pdua, Aglio A H; Malfreyt, Patrice; Malberg, Friedrich; Kirchner, Barbara; Pensado, Alfonso S

    2014-01-23

    Using molecular dynamics simulations, we have studied the structure of three 1-butyl-1-methylpyrrolidinium ionic liquids whose anions are triflate, bis(trifluoromethanesulfonyl)imide, and tris(pentafluoroethyl)trifluorophosphate. The structure of the bulk phase of the three ionic liquids has been interpreted using radial and spatial distribution functions and structure factors that allows us to characterize the morphology of the polar and nonpolar domains present in this family of liquids. The size of the polar regions depends on the anion size, whereas the morphology of the nonpolar domains is anion-independent. Furthermore, the surface ordering properties of the ionic liquids and charge and density profiles were also studied using molecular simulations. The surface tension of the liquid-vapor interfaces of these ionic liquids was also predicted from our molecular simulations. In addition, microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface suggest that the alkyl chains of the cation tend to protrude toward the vacuum, and the presence of the interface leads to a strong organization of the liquid phase in the region close to the interface. In the interfacial area, the polar regions of the ionic liquids are more structured than those in the bulk phase, whereas the opposite behavior is observed for the nonpolar regions. PMID:24383956

  11. 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 the influence of ILs on charge transport processes. Picosecond pulse radiolysis studies at BNL's Laser-Electron Accelerator Facility (LEAF) are used to identify reactive species in ionic liquids and measure their solvation and reaction rates. We and our collaborators (R. Engel (Queens College, CUNY) and S. Lall-Ramnarine, (Queensborough CC, CUNY)) develop and characterize new ionic liquids specifically designed for our radiolysis and solvation dynamics studies. IL solvation and rotational dynamics are measured by TCSPC and fluorescence upconversion measurements in the laboratory of E. W. Castner at Rutgers Univ. Investigations of radical species in irradiated ILs are carried out at ANL by I. Shkrob and S. Chemerisov using EPR spectroscopy. Diffusion rates are obtained by PGSE NMR in S. Greenbaum's lab at Hunter College, CUNY and S. Chung's lab at William Patterson U. Professor Mark Kobrak of CUNY Brooklyn College performs molecular dynamics simulations of solvation processes. A collaboration with M. Dietz at U. Wisc. Milwaukee is centered around the properties and radiolytic behavior of ionic liquids for nuclear separations. Collaborations with C. Reed (UC Riverside), D. Gabel (U. Bremen) and J. Davis (U. South Alabama) are aimed at characterizing the radiolytic and other properties of borated ionic liquids, which could be used to make fissile material separations processes inherently safe from criticality accidents.

  12. 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. Successful extraction of metal from metal oxide dissolved in Urea/ChCl (2:1) was accomplished. The current efficiencies were relatively high in both the metal deposition processes with current efficiency greater than 86% for lead and 95% for zinc. This technology will advance the metal oxide reduction process by increasing the process efficiency and also eliminate the production of CO2 which makes this an environmentally benign technology for metal extraction.

  13. 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 the influence of ILs on charge transport processes. Picosecond pulse radiolysis studies at BNL's Laser-Electron Accelerator Facility (LEAF) [1] are used to identify reactive species in ionic liquids and measure their solvation and reaction rates. IL solvation and rotational dynamics are measured by TCSPC in the laboratory of E. W. Castner at Rutgers Univ. Investigations of radical species in irradiated ILs are carried out at ANL by I. Shkrob and S. Chemerisov using EPR spectroscopy.

  14. 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.

  15. 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.

  16. Ionic Conductivity and Gas Permeability of Polymerized Ionic Liquid Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Sanoja, Gabriel; Schneider, Yanika; Modestino, Miguel; Segalman, Rachel; Joint CenterArtificial Photosynthesis Team

    2014-03-01

    Polymer membranes for many energy applications, such as solar-to-hydrogen fuel production, require ionic conductivity while acting as gas diffusion barriers. We have synthesized a diblock copolymer consisting of poly(styrene-block-(4-(2-methacrylamidoethyl)-imidazolium trifluoroacetate) by treating poly(styrene-block-histamine methacrylamide) (PS- b-PHMA) with trifluoroacetic acid. The PS block serves as the structural support while the imidazolium derivative is an ion conducting polymerized ionic liquid (PIL). Small angle X-ray scattering and transmission electron microscopy demonstrate that the block copolymer self-assembles into well-ordered nanostructures, with lamellae and hexagonally packed cylindrical morphologies. The ionic conductivities of the PS-b-PHMA materials were as high as 2 x 10-4 S/cm while an order of magnitude increase in conductivity was observed upon conversion to PS-b-PIL. The ionic conductivity of the PS-b-PIL increased by a factor of ~ 4 up to 1.2 x 10-3 S/cm as the PIL domain size increased from 20 to 40 nm. These insights allow for the rational design of high performance ion conducting membranes with even greater conductivities via precise morphological control. Additionally, the role of thermal annealing on the ionic conductivity and gas permeability of copolymer membranes was investigated.

  17. Ionic Liquids: Trends in Behavior and Miscibility with Polymers

    NASA Astrophysics Data System (ADS)

    Chen, Michelle; White, Ronald; Lipson, Jane

    2015-03-01

    Trends in polymer solution miscibility can be understood by analyzing the properties of each pure component. In this work, families of ionic liquids were characterized using the Locally Correlated Lattice (LCL) model that was previously used to study numerous polymers as well as their solutions and blends. Ionic liquids were divided into families that incorporated size variation into each of the components. The cationic species comprised members of the CnMIM (1-alkyl-3-methylimidazolium) family with n ranging from 2 to 10. The anionic component varied from BF4 to PF6 to NTf2 (bis(trifluoromethylsulfonyl)amide). Each liquid was characterized using the LCL equation of state and properties such as percent free volume and cohesive energy density were calculated. These properties were observed to be correlated with alkyl chain length and anion size within each family. Analyzing these trends points towards a fundamental understanding of ionic liquid miscibility with poly(ethylene oxide), members of the polymethacrylate family, and others. Work supported by NSF-DMR.

  18. Polymer--Ionic liquid Electrolytes for Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Ketabi, Sanaz

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

  19. Separation of fission products based on ionic liquids: Task-specific ionic liquids containing an aza-crown ether fragment

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V; Buchanan III, A C

    2005-01-01

    A new class of task-specific ionic liquids (TSILs) based on the covalent attachment of imidazolium cations to a monoaza-crown ether fragment has been synthesized and characterized. The efficacy of these TSILs for the biphasic extraction of Cs(+) and Sr(2+) from aqueous solutions has been evaluated. The extraction properties of these TSILs can be influenced by the structures of the covalently attached imidazolium cations, which highlight the possibilities to enhance or tune the selectivities of crown ethers toward target ionic species through the covalent coupling with the imidazolium cations. (c) 2005 Elsevier B.V. All rights reserved.

  20. Structure and ionic conductivity of ionic liquid embedded PEO- LiCF3SO3 polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Karmakar, A.; Ghosh, A.

    2014-08-01

    In this paper we have reported electrical and other physical properties of polyethylene oxide (PEO) - LiCF3SO3 polymer electrolytes embedded with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. The addition of the ionic liquid to PEO- LiCF3SO3 electrolyte increases the amorphous phase content considerably and decreases the glass transition temperature. The relative amounts of different ionic species present in these electrolytes have been determined. It is observed that the fraction of free anions increase with the increase of ionic liquid concentration, whereas the fraction for ion pairs and aggregates show a decreasing trend under the same condition. The ionic conductivity of the PEO- LiCF3SO3 polymer electrolyte embedded with ionic liquid is higher than that of the PEO- LiCF3SO3 electrolyte. The ionic conductivity shows a transition around 323 K. The ionic conductivity above 323 K exhibits Arrhenius behavior with an activation energy, which decreases with the increase of ionic liquid concentration. However, below 323 K the conductivity shows Vogel-Tamman-Fulcher (VTF) type behavior.

  1. Free volume dependence of an ionic molecular rotor in Fluoroalkylphosphate (FAP) based ionic liquids

    NASA Astrophysics Data System (ADS)

    Singh, Prabhat K.; Mora, Aruna K.; Nath, Sukhendu

    2016-01-01

    The emission properties of Thioflavin-T (ThT), a cationic molecular rotor, have been investigated in two fluoroalkylphosphate ([FAP]) anion based ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate and 1-(2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, over a wide temperature range. The micro-viscosities of ionic liquids around ThT, measured from the emission quantum yield, are found to be quite different from their bulk viscosities. The temperature dependence of the viscosity and the emission quantum yield reveals that, despite the very low shear viscosity of these ILs, the non-radiative torsional relaxation has a strong dependence on the free volume of these [FAP] anion based ILs.

  2. 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

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

    PubMed

    Passos, Helena; Lus, Andreia; Coutinho, Joo 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

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

    PubMed

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

    2016-03-14

    Ionic liquids (ILs), which have widely tunable structural motifs and intermolecular interactions with solutes, have been proposed as possible carbon capture media. To inform the choice of an optimal ionic liquid system, it can be useful to understand the details of dynamics and interactions on fundamental time scales (femtoseconds to picoseconds) of dissolved gases, particularly carbon dioxide (CO2), within the complex solvation structures present in these uniquely organized materials. The rotational and local structural fluctuation dynamics of CO2 in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2) were investigated by using ultrafast infrared spectroscopy to interrogate the CO2 asymmetric stretch. Polarization-selective pump probe measurements yielded the orientational correlation function of the CO2 vibrational transition dipole. It was found that reorientation of the carbon dioxide occurs on 3 time scales: 0.91 ± 0.03, 8.3 ± 0.1, 54 ± 1 ps. The initial two are attributed to restricted wobbling motions originating from a gating of CO2 motions by the IL cations and anions. The final (slowest) decay corresponds to complete orientational randomization. Two-dimensional infrared vibrational echo (2D IR) spectroscopy provided information on structural rearrangements, which cause spectral diffusion, through the time dependence of the 2D line shape. Analysis of the time-dependent 2D IR spectra yields the frequency-frequency correlation function (FFCF). Polarization-selective 2D IR experiments conducted on the CO2 asymmetric stretch in the parallel- and perpendicular-pumped geometries yield significantly different FFCFs due to a phenomenon known as reorientation-induced spectral diffusion (RISD), revealing strong vector interactions with the liquid structures that evolve slowly on the (independently measured) rotation time scales. To separate the RISD contribution to the FFCF from the structural spectral diffusion contribution, the previously developed first order Stark effect RISD model is reformulated to describe the second order (quadratic) Stark effect-the first order Stark effect vanishes because CO2 does not have a permanent dipole moment. Through this analysis, we characterize the structural fluctuations of CO2 in the ionic liquid solvation environment, which separate into magnitude-only and combined magnitude and directional correlations of the liquid's time dependent electric field. This new methodology will enable highly incisive comparisons between CO2 dynamics in a variety of ionic liquid systems. PMID:26979696

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Ionic liquids (ILs), which have widely tunable structural motifs and intermolecular interactions with solutes, have been proposed as possible carbon capture media. To inform the choice of an optimal ionic liquid system, it can be useful to understand the details of dynamics and interactions on fundamental time scales (femtoseconds to picoseconds) of dissolved gases, particularly carbon dioxide (CO2), within the complex solvation structures present in these uniquely organized materials. The rotational and local structural fluctuation dynamics of CO2 in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2) were investigated by using ultrafast infrared spectroscopy to interrogate the CO2 asymmetric stretch. Polarization-selective pump probe measurements yielded the orientational correlation function of the CO2 vibrational transition dipole. It was found that reorientation of the carbon dioxide occurs on 3 time scales: 0.91 ± 0.03, 8.3 ± 0.1, 54 ± 1 ps. The initial two are attributed to restricted wobbling motions originating from a gating of CO2 motions by the IL cations and anions. The final (slowest) decay corresponds to complete orientational randomization. Two-dimensional infrared vibrational echo (2D IR) spectroscopy provided information on structural rearrangements, which cause spectral diffusion, through the time dependence of the 2D line shape. Analysis of the time-dependent 2D IR spectra yields the frequency-frequency correlation function (FFCF). Polarization-selective 2D IR experiments conducted on the CO2 asymmetric stretch in the parallel- and perpendicular-pumped geometries yield significantly different FFCFs due to a phenomenon known as reorientation-induced spectral diffusion (RISD), revealing strong vector interactions with the liquid structures that evolve slowly on the (independently measured) rotation time scales. To separate the RISD contribution to the FFCF from the structural spectral diffusion contribution, the previously developed first order Stark effect RISD model is reformulated to describe the second order (quadratic) Stark effect—the first order Stark effect vanishes because CO2 does not have a permanent dipole moment. Through this analysis, we characterize the structural fluctuations of CO2 in the ionic liquid solvation environment, which separate into magnitude-only and combined magnitude and directional correlations of the liquid's time dependent electric field. This new methodology will enable highly incisive comparisons between CO2 dynamics in a variety of ionic liquid systems.

  6. 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

    2016-01-20

    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

  7. Keggin-type polyoxometalate-based ionic liquid gels.

    PubMed

    Huang, Tianpei; Tian, Naiqin; Wu, Qingyin; Yan, Wenfu

    2015-06-14

    A series of reversible phase transformation ammonium- and phosphonium-based polyoxometalate ionic liquid (POM-IL) gels were synthesized and studied with a focus on the correlation between their physicochemical properties and their chemical structure. The products were successfully characterized by IR, UV, XRD and TG-DTA, and their ionic conductivities were measured. The Keggin-type heteropolyanion clusters decorated with long alkyl chains demonstrated a tendency to exhibit a gel state at room temperature, while all the gels transformed into liquids after heating and then recovered after cooling. With a decrease in the alkyl chain length, a significant improvement in the thermal stability and conductivity of the ammonium-based POM-IL gels can be achieved. Moreover, compared with the corresponding ammonium compound, phosphonium-based POM-IL gel was found to be more stable at high temperature and exhibited better conductivity. PMID:25947074

  8. 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.

  9. Sparingly soluble pesticide dissolved in ionic liquid aqueous.

    PubMed

    Fan, Tengfei; Wu, Xuemin; Peng, Qingrong

    2014-10-01

    Ionic liquids may be considered as "environment-friendly solvents" for sparingly soluble pesticides. In this study, a series of aqueous ionic liquids (ILs) with different cations and different anions was used as environment-friendly alternative to harmful organic solvents sparingly dissolved in soluble pesticides (metolachlor, acetochlor, clethodim, thiamethoxam, and prochloraz). The aggregation behavior of aqueous ILs was investigated through surface tension measurement. Minimum area per IL molecule (Amin) values from the surface tension measurement showed that alkyl chain length and the halide anions strongly affect the aggregation behavior of ILs and the solubilization of pesticides. The solubility of metolachlor, acetochlor, clethodim, thiamethoxam, nitenpyram, and prochloraz in aqueous ILs increased. More importantly, the solubility of prochloraz in [C10mim][I] became 5771-fold higher than that in pure water. The substantially enhanced solubility of the above pesticides proved that aqueous ILs are promising environment-friendly solvents for pesticides that are commercially processed in emulsifiable concentrate (EC) formulation. PMID:25222470

  10. Carbon films produced from ionic liquid carbon precursors

    SciTech Connect

    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 %.

  11. 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.

  12. 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.

  13. 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's Laser-Electron Accelerator Facility (LEAF) are used to identify reactive species in ionic liquids and measure their solvation and reaction rates. We and our collaborators (R. Engel (Queens College, CUNY) and S. Lall-Ramnarine, (Queensborough CC, CUNY)) develop and characterize new ionic liquids specifically designed for our radiolysis and solvation dynamics studies. IL solvation and rotational dynamics are measured by TCSPC and fluorescence upconversion measurements in the laboratory of E. W. Castner at Rutgers Univ. Investigations of radical species in irradiated ILs are carried out at ANL by I. Shkrob and S. Chemerisov using EPR spectroscopy. Diffusion rates are obtained by PGSE NMR in S. Greenbaum's lab at Hunter College, CUNY and S. Chung's lab at William Patterson U. Professor Mark Kobrak of CUNY Brooklyn College performs molecular dynamics simulations of solvation processes. A collaboration with M. Dietz and coworkers at ANL is centered around the properties and radiolytic behavior of ionic liquids for nuclear separations. Collaborations with C. Reed (UC Riverside), D. Gabel (U. Bremen) and J. Davis (U. South Alabama) are aimed at characterizing the radiolytic and other properties of borated ionic liquids, which could be used to make fissile material separations processes inherently safe from criticality accidents.

  14. Synthesis and characterization of 5-cyanotetrazolide-based ionic liquids.

    PubMed

    Bergholz, Timm; Oelkers, Benjamin; Huber, Benedikt; Roling, Bernhard; Sundermeyer, Jrg

    2015-02-01

    New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5-cyanotetrazolide anion [C2 N5 ](-) are reported. Depending on the nature of cation-anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230?C, an electrochemical window of 4.5?V, a viscosity of 25?mPa?s at 20?C, and an ionic conductivity of 5.4 mS cm(-1) at 20?C for the IL 1-butyl-1-methylpyrrolidinium 5-cyanotetrazolide [BMPyr][C2 N5 ]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium-ion batteries. PMID:25504790

  15. 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 Brnsted 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.

  16. 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.

  17. Hopping conduction via ionic liquid induced silicon surface states

    NASA Astrophysics Data System (ADS)

    Nelson, J.; Reich, K. V.; Sammon, M.; Shklovskii, B. I.; Goldman, A. M.

    2015-08-01

    In order to clarify the physics of the gating of solids by ionic liquids (ILs) we have gated lightly doped p -Si, which is so well studied that it can be called the "hydrogen atom of solid state physics" and can be used as a test bed for ionic liquids. We explore the case where the concentration of induced holes at the Si surface is below 1012cm-2 , hundreds of times smaller than record values. We find that in this case an excess negative ion binds a hole on the interface between the IL and Si becoming a surface acceptor. We study the surface conductance of holes hopping between such nearest neighbor acceptors. Analyzing the acceptor concentration dependence of this conductivity, we find that the localization length of a hole is in reasonable agreement with our direct variational calculation of its binding energy. The observed hopping conductivity resembles that of well studied Na+ implanted Si MOSFETs.

  18. 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

  19. Pressure-responsive mesoscopic structures in room temperature ionic liquids.

    PubMed

    Russina, Olga; Celso, Fabrizio Lo; Triolo, Alessandro

    2015-11-28

    Among the most spectacular peculiarities of room temperature ionic liquids, their mesoscopically segregated structural organization keeps on attracting attention, due to its major consequences for the bulk macroscopic properties. Herein we use molecular dynamics simulations to explore the nm-scale architecture in 1-octyl-3-methylimidazolium tetrafluoroborate, as a function of pressure. This study reveals an intriguing new feature: the mesoscopic segregation in ionic liquids is characterized by a high level of pressure-responsiveness, which progressively vanishes upon application of high enough pressure. These results are in agreement with recent X-ray scattering data and are interpreted in terms of the microscopic organization. This new feature might lead to new methods of developing designer solvents for enhanced solvation capabilities and selectivity. PMID:26498176

  20. Isomer effect of propanol on liquid-liquid equilibrium in hydrophobic room-temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Ozawa, Shinichiro; Kishimura, Hiroaki; Kitahira, Shota; Tamatani, Kentaro; Hirayama, Kentaro; Abe, Hiroshi; Yoshimura, Yukihiro

    2014-10-01

    The cloud-point temperature determined the liquid-liquid phase equilibrium (LLE) of binary systems comprising hydrophobic room-temperature ionic liquids (RTILs) and propanol. The RTILs were 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [Cxmim][TFSI] (2 ? x ? 10). Upper critical solution temperatures in LLE are inversely proportional to the Cxmim+ cation alkyl chain length, x. The propanol isomer effect indicates the critical alkyl chain length (xcritical = 6-7). UNIQUAC model determined the interaction parameters (with crossing points at x = 6). In pure RTILs, conformation stability of TFSI- by Raman spectroscopy changed between x = 6 and 7, corresponding to the simulation-determined 90-torsion angle at x = 6.

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

    SciTech Connect

    Dr. R. G. Reddy

    2007-09-01

    The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient (0.40). Nucleation phenomena involved in aluminum deposition on copper in AlCl3-BMIMCl electrolyte was found to be instantaneous followed by diffusion controlled three-dimensional growth of nuclei. Diffusion coefficient (Do) of the electroactive species Al2Cl7¯ ion was in the range from 6.5 to 3.9×10–7 cm2∙s–1 at a temperature of 30°C. Relatively little research efforts have been made toward the fundamental understanding and modeling of the species transport and transformation information involved in ionic liquid mixtures, which eventually could lead to quantification of electrochemical properties. Except that experimental work in this aspect usually is time consuming and expensive, certain characteristics of ionic liquids also made barriers for such analyses. Low vapor pressure and high viscosity make them not suitable for atomic absorption spectroscopic measurement. In addition, aluminum electrodeposition in ionic liquid electrolytes are considered to be governed by multi-component mass, heat and charge transport in laminar and turbulent flows that are often multi-phase due to the gas evolution at the electrodes. The kinetics of the electrochemical reactions is in general complex. Furthermore, the mass transfer boundary layer is about one order of magnitude smaller than the thermal and hydrodynamic boundary layer (Re=10,000). Other phenomena that frequently occur are side reactions and temperature or concentration driven natural convection. As a result of this complexity, quantitative knowledge of the local parameters (current densities, ion concentrations, electrical potential, temperature, etc.) is very difficult to obtain. This situation is a serious obstacle for improving the quality of products, efficiency of manufacturing and energy consumption. The gap between laboratory/batch scale processing with global process control and nanoscale deposit surface and materials specifications needs to be bridged. A breakthrough can only be realized if on each scale the occurring phenomena are understood and quantified. Multiscale numerical modeling nevertheless can help to bridge this gap. In conjunction with various scale experimental efforts, this project was aim to construct the basis for a strategy for innovation, by developing a generally applicable modeling methodology for understanding and controlling the electrochemical processes of aluminum electrodeposition in ionic liquids with the unifying characteristic that they are based on charge-driven mass transfer. The approaches developed in this project will not only be essential for the mass production of aluminum on any pilot scale or industrial level production processes, leading to the development of a new aluminum production technology, but also bring significant benefits to the society in terms of saving energy, reducing pollutants emission and recovering valuable metals.

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

    SciTech Connect

    Dr. Ramana G. Reddy

    2009-01-31

    EXECUTIVE SUMMARY The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient  = 0.40. Nucleation phenomena involved in aluminum deposition on copper in AlCl3-BMIMCl electrolyte was found to be instantaneous followed by diffusion controlled three-dimensional growth of nuclei. Diffusion coefficient (Do) of the electroactive species Al2Cl7¯ ion was in the range from 6.5 to 3.9×10–7 cm2∙s–1 at a temperature of 30°C. Relatively little research efforts have been made toward the fundamental understanding and modeling of the species transport and transformation information involved in ionic liquid mixtures, which eventually could lead to quantification of electrochemical properties. Except that experimental work in this aspect usually is time consuming and expensive, certain characteristics of ionic liquids also made barriers for such analyses. Low vapor pressure and high viscosity make them not suitable for atomic absorption spectroscopic measurement. In addition, aluminum electrodeposition in ionic liquid electrolytes are considered to be governed by multi-component mass, heat and charge transport in laminar and turbulent flows that are often multi-phase due to the gas evolution at the electrodes. The kinetics of the electrochemical reactions is in general complex. Furthermore, the mass transfer boundary layer is about one order of magnitude smaller than the thermal and hydrodynamic boundary layer (ReL≈10,000). Other phenomena that frequently occur are side reactions and temperature or concentration driven natural convection. As a result of this complexity, quantitative knowledge of the local parameters (current densities, ion concentrations, electrical potential, temperature, etc.) is very difficult to obtain. This situation is a serious obstacle for improving the quality of products, efficiency of manufacturing and energy consumption. The gap between laboratory/batch scale processing with global process control and nanoscale deposit surface and materials specifications needs to be bridged. A breakthrough can only be realized if on each scale the occurring phenomena are understood and quantified. Multiscale numerical modeling nevertheless can help to bridge this gap. In conjunction with various scale experimental efforts, this project was aim to construct the basis for a strategy for innovation, by developing a generally applicable modeling methodology for understanding and controlling the electrochemical processes of aluminum electrodeposition in ionic liquids with the unifying characteristic that they are based on charge-driven mass transfer. The approaches developed in this project will not only be essential for the mass production of aluminum on any pilot scale or industrial level production processes, leading to the development of a new aluminum production technology, but also bring significant benefits to the society in terms of saving energy, reducing pollutants emission and recovering valuable metals.

  3. HMDO-promoted peptide and protein synthesis in ionic liquids.

    PubMed

    Duan, Jianli; Sun, Yao; Chen, Hao; Qiu, Guofu; Zhou, Haibing; Tang, Ting; Deng, Zixin; Hong, Xuechuan

    2013-07-19

    Hexamethyldisiloxane (HMDO) has been developed to efficiently promote the metal-free direct coupling of an amino function of one cysteine-free peptide or protein and a C-terminal thioester of the second peptide in ionic liquids. The amide-coupling reaction proceeds smoothly under mild conditions to afford the corresponding products in good to excellent yields (63-94%). Peptide couplings were also achieved using in-situ-generated thioesters by the thioesterification of oxo esters. PMID:23829697

  4. 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.

  5. Photochemical oxidation of water and reduction of polyoxometalate anions at interfaces of water with ionic liquids or diethylether

    PubMed Central

    Bernardini, Gianluca; Wedd, Anthony G.; Zhao, Chuan; Bond, Alan M.

    2012-01-01

    Photoreduction of [P2W18O62]6-, [S2Mo18O62]4-, and [S2W18O62]4- polyoxometalate anions (POMs) and oxidation of water occurs when waterionic liquid and waterdiethylether interfaces are irradiated with white light (275750nm) or sunlight. The ionic liquids (ILs) employed were aprotic ([Bmim]X; Bmim=(1-butyl-3-methylimidazolium,X=BF4,PF6) and protic (DEAS=diethanolamine hydrogen sulphate; DEAP=diethanolamine hydrogen phosphate). Photochemical formation of reduced POMs at both thermodynamically stable and unstable waterIL interfaces led to their initial diffusion into the aqueous phase and subsequent extraction into the IL phase. The mass transport was monitored visually by color change and by steady-state voltammetry at microelectrodes placed near the interface and in the bulk solution phases. However, no diffusion into the organic phase was observed when [P2W18O62]6- was photo-reduced at the waterdiethylether interface. In all cases, water acted as the electron donor to give the overall process: 4POM+2H2O+h??4POM-+4H++O2. However, more highly reduced POM species are likely to be generated as intermediates. The rate of diffusion of photo-generated POM- was dependent on the initial concentration of oxidized POM and the viscosity of the IL (or mixed phase system produced in cases in which the interface is thermodynamically unstable). In the water-DEAS system, the evolution of dioxygen was monitored in situ in the aqueous phase by using a Clark-type oxygen sensor. Differences in the structures of bulk and interfacial water are implicated in the activation of water. An analogous series of reactions occurred upon irradiation of solid POM salts in the presence of water vapor. PMID:22753501

  6. Photochemical oxidation of water and reduction of polyoxometalate anions at interfaces of water with ionic liquids or diethylether.

    PubMed

    Bernardini, Gianluca; Wedd, Anthony G; Zhao, Chuan; Bond, Alan M

    2012-07-17

    Photoreduction of [P(2)W(18)O(62)](6-), [S(2)Mo(18)O(62)](4-), and [S(2)W(18)O(62)](4-) polyoxometalate anions (POMs) and oxidation of water occurs when water-ionic liquid and water-diethylether interfaces are irradiated with white light (275-750 nm) or sunlight. The ionic liquids (ILs) employed were aprotic ([Bmim]X; Bmim = (1-butyl-3-methylimidazolium, X = BF(4), PF(6)) and protic (DEAS = diethanolamine hydrogen sulphate; DEAP = diethanolamine hydrogen phosphate). Photochemical formation of reduced POMs at both thermodynamically stable and unstable water-IL interfaces led to their initial diffusion into the aqueous phase and subsequent extraction into the IL phase. The mass transport was monitored visually by color change and by steady-state voltammetry at microelectrodes placed near the interface and in the bulk solution phases. However, no diffusion into the organic phase was observed when [P(2)W(18)O(62)](6-) was photo-reduced at the water-diethylether interface. In all cases, water acted as the electron donor to give the overall process: 4POM + 2H(2)O + h? ? 4POM(-) + 4H(+) + O(2). However, more highly reduced POM species are likely to be generated as intermediates. The rate of diffusion of photo-generated POM(-) was dependent on the initial concentration of oxidized POM and the viscosity of the IL (or mixed phase system produced in cases in which the interface is thermodynamically unstable). In the water-DEAS system, the evolution of dioxygen was monitored in situ in the aqueous phase by using a Clark-type oxygen sensor. Differences in the structures of bulk and interfacial water are implicated in the activation of water. An analogous series of reactions occurred upon irradiation of solid POM salts in the presence of water vapor. PMID:22753501

  7. 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

  8. Plasma electrochemistry in ionic liquids: deposition of copper nanoparticles.

    PubMed

    Brettholle, M; Hfft, O; Klarhfer, L; Mathes, S; Maus-Friedrichs, W; Zein El Abedin, S; Krischok, S; Janek, J; Endres, F

    2010-02-28

    We report on the synthesis of copper nanoparticles in two different water- and air-stable ionic liquids using plasma electrochemical deposition. The copper nanoparticles were deposited in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm]Tf(2)N). To get information on the dimensions of the particles made, we have applied in situ transmission electron microscopy (TEM) (particles in ionic liquid). The chemical composition was investigated by ex situ X-ray photoelectron spectroscopy (XPS). We found that the copper particles produced in [Py(1,4)]Tf(2)N were larger in size compared to the particles obtained in [EMIm] Tf(2)N (roughly 20 vs. 10 nm). The chemical composition of the particle surface differs too. In both cases the particles are partly oxidised leading to a CuO shell, but the particles obtained in [Py(1,4)]Tf(2)N carry a lot of residues from the ionic liquid. PMID:20145839

  9. 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

  10. Glass transition of ionic liquids under high pressure.

    PubMed

    Ribeiro, Mauro C C; Pdua, Aglio A H; Gomes, Margarida F Costa

    2014-06-28

    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, TV(?), 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 ? over this range of density, a reasonable agreement has been found for the ? 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. PMID:24985661

  11. 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

  12. 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.

  13. 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.

  14. Charge ordering and intermediate range order in ammonium ionic liquids.

    PubMed

    Siqueira, Leonardo J A; Ribeiro, Mauro C C

    2011-11-28

    Molecular dynamics simulations were performed for ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion, [NTf(2)], and ammonium cations with increasing length of the alkyl chain and ether functionalized chain. The signature of charge ordering is a sharp peak in the charge-charge structure factor, S(qq)(k), whose intensity is barely affected for longer carbon chain in tetraalkylammonium systems, but decreases in ether functionalized ionic liquids. The first sharp diffraction peak (FSDP) and the corresponding intermediate range order (IRO) are observed in the total S(k) of ionic liquids containing ammonium cations with relatively long chains. The intensity of the FSDP is lower in the total S(k) of the ether derivative in comparison with the tetraalkylammonium counterpart of the same chain length. It is shown that the nature of the IRO is structural heterogeneity of polar and non-polar domains, even though domains defined by chain interactions in the ether derivatives become more polar. Charge correlation in the ether derivative is modified because cations can be coordinated by oxygen atoms of the ether functionalized chain of neighboring cations. PMID:22128942

  15. 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.

  16. Straightforward synthesis of the Brnsted acid hfipOSO3H and its application for the synthesis of protic ionic liquids.

    PubMed

    Beichel, Witali; Panzer, Johann M U; Htty, Julian; Ye, Xiaowei; Himmel, Daniel; Krossing, Ingo

    2014-06-23

    The easily accessible hexafluoroisopropoxysulfuric acid (1, hfipOSO3H; hfip = C(H)(CF3)2) was synthesized by the reaction of hexafluoroisopropanol and chlorosulfonic acid on the kilogram scale and isolated in 98?% yield. The calculated gas-phase acidity (GA) value of 1 is 58?kJ?mol(-1) lower in ?G than that of sulfuric acid (GA value determined by a CCSD(T)-MP2 compound method). Considering the gas-phase dissociation constant as a measure for the intrinsic molecular acid strength, a hfipOSO3H molecule is more than ten orders of magnitude more acidic than a H2SO4 molecule. The acid is a liquid at room temperature, distillable at reduced pressure, stable for more than one year in a closed vessel, reactive towards common solvents, and decomposes above 180?C. It is a versatile compound for further applications, such as the synthesis of ammonium- and imidazolium-based air- and moisture-stable protic ionic liquids (pILs). Among the six synthesized ionic compounds, five are pILs with melting points below 100?C and three of them are liquids at nearly room temperature. The conductivities and viscosities of two representative ILs were investigated in terms of Walden plots, and the pILs were found to be little associated ILs, comparable to conventional aprotic ILs. PMID:24862292

  17. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    NASA Astrophysics Data System (ADS)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Cabeza, Oscar; Fedorov, Maxim; Lynden-Bell, Ruth M.; Gallego, Luis J.; Varela, Luis M.

    2015-09-01

    We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF6]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO3]- and [PF6]- anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca2+ cations. No qualitative difference with monovalent cations was found in what solvation is concerned, which suggests that no enhanced reduction of the mobility of these cations and their complexes in ILs respective to those of monovalent cations is to be expected.

  18. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids.

    PubMed

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Cabeza, Oscar; Fedorov, Maxim; Lynden-Bell, Ruth M; Gallego, Luis J; Varela, Luis M

    2015-09-28

    We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF6]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO3](-) and [PF6](-) anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca(2+) cations. No qualitative difference with monovalent cations was found in what solvation is concerned, which suggests that no enhanced reduction of the mobility of these cations and their complexes in ILs respective to those of monovalent cations is to be expected. PMID:26429024

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

    PubMed

    Likhanova, Natalya V; Guzmn-Lucero, Diego; Flores, Eugenio A; Garca, Paloma; Domnguez-Aguilar, Marco A; Palomeque, Jorge; Martnez-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

  20. 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.

  1. Shear relaxation of ammonium- and phosphonium-based ionic liquids with oxyethylene chain

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Tsuyoshi; Mikawa, Ken-ichi; Koda, Shinobu; Fukazawa, Hiroki; Shirota, Hideaki

    2012-01-01

    Frequency-dependent shear viscosities of ammonium- and phosphonium-based ionic liquids with an oxyethylene chain were determined between 5 and 205 MHz, and compared with those of corresponding ionic liquids with an alkyl chain. The shear relaxation spectra show that the substitution of the alkyl chain with the oxyethylene one lowers shear viscosity through the reduction of relaxation time, which is attributed to the higher flexibility of the latter. Comparing the relaxation spectra of ionic liquids with those of non-ionic ones, higher shear viscosities of ionic liquids are ascribed to the larger high-frequency shear modulus due to the interionic Coulombic interaction.

  2. Unusual solvatochromic absorbance probe behaviour within mixtures of poly(ethylene glycol)-400+ionic liquid, [bmim][Tf2N].

    PubMed

    Ali, Anwar; Ali, Maroof; Malik, Nisar Ahmad; Uzair, Sahar

    2014-01-01

    The potentially green solvents made up of ionic liquids (ILs) and poly(ethylene glycols) may have wide range of the applications in many chemical and biochemical fields. In the present work, solvatochromic absorbance probe behaviour is used to assess the physicochemical properties of the mixtures composed of PEG-400+IL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][Tf2N]. Lowest energy intramolecular charge-transfer absorbance maxima of a betaine dye, i.e., E(T)(N), indicates the dipolarity/polarizability and/or hydrogen-bond donating (HBD) acidity of the [bmim][Tf2N]+PEG-400 mixtures to be even higher than that of neat [bmim][Tf2N], the solution component with higher dipolarity/polarizability and/or HBD acidity. Dipolarity/polarizability (?(?)) obtained separately from the electronic absorbance response of probe N,N-diethyl-4-nitroaniline, and the HBD acidity (?) of PEG-400+[bmim][Tf2N] mixtures are also observed to be anomalously high. A comparative study of the PEG+IL mixtures has also been done with PEG-400+molecular organic solvents (protic polar [methanol], aprotic polar [N,N-dimethylformamide], and non polar, [benzene]) mixtures, but these mixtures do not show this type of unusual behaviour. A four-parameter simplified combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation is shown to satisfactorily predict the solvatochromic parameters within PEG-400+different solvent mixtures. PMID:24280298

  3. A novel hydroxylamine ionic liquid salt resulting from the stabilization of NH2OH by a SO3H-functionalized ionic liquid.

    PubMed

    Li, Zhihui; Yang, Qiusheng; Qi, Xudong; Xu, Yuanyuan; Zhang, Dongsheng; Wang, Yanji; Zhao, Xinqiang

    2015-02-01

    A SO3H-functionalized ionic liquid was used as an alternative to conventional inorganic acids in hydroxylamine stabilization, leading to the formation of a novel hydroxylamine ionic liquid salt that exhibits improved thermal stability and reactivity in the one-step, solvent-free synthesis of caprolactam in comparison with hydroxylamine hydrochloride and hydroxylamine sulfate. PMID:25531208

  4. Imidazolium-based poly(ionic liquid)s as new alternatives for CO2 capture.

    PubMed

    Privalova, Elena I; Karjalainen, Erno; Nurmi, Mari; Mki-Arvela, Pivi; Ernen, Kari; Tenhu, Heikki; Murzin, Dmitry Yu; Mikkola, Jyri-Pekka

    2013-08-01

    Solid imidazolium-based poly(ionic liquid)s with variable molecular weights that contain the poly[2-(1-butylimidazolium-3-yl)ethyl methacrylate] (BIEMA) cation and different counter anions were evaluated in terms of CO2 capture and compared with classical ionic liquids with similar counter anions. In addition to poly(ionic liquid)s with often-applied ions such as BF4 (-) , PF6 (-) , NTf2 (-) , trifluoromethanesulfonate (OTf(-) ) and Br(-) , for the first time [BIEMA][acetate] was synthesised, which revealed a remarkably high CO2 sorption performance that exceeded the poly(ionic liquid)s studied previously on average by a factor of four (12.46 mg gPIL (-1) ). This study provides an understanding of the factors that affect CO2 sorption and a comparison of the CO2 capture efficiency with the frequently used sorbents. Moreover, all the studied sorbents were reusable if regenerated under carefully selected conditions and can be considered as suitable candidates for CO2 sorption. PMID:23881741

  5. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  7. Solvent Extraction of Sr2+ and Cs+ Based on Hydrophobic Protic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Luo, Huimin; Yu, Miao; Dai, Sheng

    2007-06-01

    A series of new hydrophobic and protic alkylammonium ionic liquids with bis(trifluoromethylsulfonyl) imide or bis(perfluoroethylsulfonyl)imide as conjugated anions was synthesized in a one-pot reaction with a high yield. In essence our synthesis method involves the combination of neutralization and metathesis reactions. Some of these hydrophobic and protic ionic liquids were liquids at room temperature and therefore investigated as new extraction media for separation of Sr2+ and Cs+ from aqueous solutions. An excellent extraction efficiency was found for some of these ionic liquids using dicyclohexano-18-crown-6 and calix[4]arene-bis(tert-octylbenzo-crown-6) as extractants. The observed enhancement in the extraction efficiency can be attributed to the greater hydrophilicity of the cations of the protic ionic liquids. The application of the protic ionic liquids as new solvent systems for solvent extraction opens up a new avenue in searching for simple and efficient ionic liquids for tailored separation processes.

  8. 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.

  9. Hg⁰ removal from flue gas by ionic liquid/H₂O₂.

    PubMed

    Cheng, Guangwen; Bai, Bofeng; Zhang, Qiang; Cai, Ming

    2014-09-15

    1-Alkyl-3-methylimidazolium chloride ionic liquids ([Cnmim] Cl, n=4, 6, 8) were prepared. The ionic liquid was then mixed with hydrogen peroxide (H2O2) to form an absorbent. The Hg(0) removal performance of the absorbent was investigated in a gas/liquid scrubber using simulated flue gas. It was found that the ionic liquid/H2O2 mixture was an excellent absorbent and could be used to remove Hg(0) from flue gas. When the mass ratio of H2O2 to ionic liquid was 0.5, the absorbent showed high Hg(0) removal efficiency (up to 98%). The Hg(0) removal efficiency usually increased with the absorption temperature, while decreased with the increase of alkyl chain length in ionic liquid molecule. The Hg(0) removal mechanism involved with Hg(0) oxidation by H2O2 and Hg(2+) transfer from aqueous phase to ionic liquid phase. PMID:25240646

  10. Liquid-liquid equilibrium of cholinium-derived bistriflimide ionic liquids with water and octanol.

    PubMed

    Costa, Anabela J L; Soromenho, Mrio R C; Shimizu, Karina; Marrucho, Isabel M; Esperana, Jos M S S; Canongia Lopes, J N; Rebelo, Lus Paulo N

    2012-08-01

    The liquid-liquid equilibria of mixtures of cholinum-based ionic liquids (N-alkyl-N,N-dimethylhydroxyethylammonium bis(trifluoromethane)sulfonylimide, [N(11n2OH)][Ntf(2)], n = 1, 2, 3, 4, and 5) plus water or 1-octanol were investigated at atmospheric pressure over the entire composition range. The experiments were conducted between 265 and 385 K using the cloud-point method. The systems exhibit phase diagrams consistent with the existence of upper critical solution temperatures. The solubility of [N(1 1 n 2OH)][Ntf(2)] in water is lower for cations with longer alkyl side chains (larger n values). The corresponding trend in the octanol mixtures is reversed. The ([N(1 1 1 2OH)][Ntf(2)] + water + octanol) ternary system shows triple liquid-liquid immiscibility at room temperature and atmospheric pressure. A combined analytic/synthetic method was used to estimate the corresponding phase diagram under those conditions. Auxiliary molecular dynamics simulation data were used to interpret the experimental results at a molecular level. PMID:22770438

  11. Nanostructure of an ionic liquid-glycerol mixture.

    PubMed

    Murphy, Thomas; Hayes, Robert; Imberti, Silvia; Warr, Gregory G; Atkin, Rob

    2014-07-14

    The nanostructure of a 50?:?50 vol% mixture of glycerol and ethylammonium formate (EAF), a protic ionic liquid (IL), has been investigated using neutron diffraction and empirical potential structure refinement (EPSR) fits. EPSR fits reveal that the mixture is nanostructured. Electrostatic interactions between IL charge groups leads to the formation of ionic regions. These solvophobically repel cation alkyl groups which cluster together to form apolar domains. The polar glycerol molecules are preferentially incorporated into the charged domains, and form hydrogen bonds with EAF groups rather than with other glycerol molecules. However, radial distribution functions reveal that glycerol molecules pack around each other in a fashion similar to that found in pure glycerol. This suggests that a glycerol channel runs through the ionic domain of EAF. The absence of significant glycerol-glycerol hydrogen bonding indicates that glycerol molecules are able to span the polar domain, bridging EAF charge groups. Glycerol can adopt six distinct conformations. The distribution of conformers in the EAF mixture is very different to that found in the pure liquid because hydrogen bonds form with EAF rather than with other glycerol molecules, which imparts different packing constraints. PMID:24871824

  12. 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

  13. Ion-pair evaporation from ionic liquid clusters.

    PubMed

    Hogan, Christopher J; Fernandez de la Mora, Juan

    2010-08-01

    A differential mobility analyzer (DMA) is used in atmospheric pressure N(2) to select a narrow range of electrical mobilities from a complex mix of cluster ions of composition (CA)(n)(C(+))(z). The clusters are introduced into the N(2) gas by electrospraying concentrated (approximately 20 mM) acetonitrile solutions of ionic liquids (molten salts) of composition CA (C(+) = cation, A(-) = anion). Mass analysis of these mobility-selected ions reveals the occurrence of individual neutral ion-pair evaporation events from the smallest singly charged clusters: (CA)(n)C(+)-->(CA)(n-1)C(+)+CA. Although bulk ionic liquids are effectively involatile at room temperature, up to six sequential evaporation events are observed. Because this requires far more internal energy than available in the original clusters, substantial heating (approximately 10 eV) must take place in the ion guides leading to the mass analyzer. The observed increase in IL evaporation rate with decreasing size is drastic, in qualitative agreement with the exponential vapor pressure dependence predicted by Kelvin's formula. A single evaporation event is barely detectable at n = 13, while two or more are prominent for n < or = 9. Magic number clusters (CA)(4)C(+) with singularly low volatilities are found in three of the four ionic liquids studied. Like their recently reported liquid phase prenucleation cluster analogs, these magic number clusters could play a key role as gas-phase nucleation seeds. All the singularly involatile clusters seen are cations, which may help understand commonly observed sign effects in ion-induced nucleation. No other charge-sign asymmetry is seen on cluster evaporation. PMID:20447834

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

    PubMed

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

    2010-03-19

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

  15. 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

  16. Chemistry of polynuclear transition-metal complexes in ionic liquids.

    PubMed

    Ahmed, Ejaz; Ruck, Michael

    2011-10-01

    Transition-metal chemistry in ionic liquids (IL) has achieved intrinsic fascination in the last few years. The use of an IL as environmental friendly solvent, offers many advantages over traditional materials synthesis methods. The change from molecular to ionic reaction media leads to new types of materials being accessible. Room-temperature IL have been found to be excellent media for stabilising transition-metal clusters in solution and to crystallise homo- and heteronuclear transition-metal complexes and clusters. Furthermore, the use of IL as solvent provides the option to replace high-temperature routes, such as crystallisation from the melt or gas-phase deposition, by convenient room- or low-temperature syntheses. Inorganic IL composed of alkali metal cations and polynuclear transition-metal cluster anions are also known. Each of these areas will be discussed briefly in this contribution. PMID:21743925

  17. 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

  18. Structural transitions of CTAB micelles in a protic ionic liquid.

    PubMed

    Lpez-Barrn, Carlos R; Wagner, Norman J

    2012-09-01

    Micellar solutions of hexadecyltrimethylammonium bromide (CTAB) in a protic ionic liquid, ethylammonium nitrate (EAN), are studied by shear rheology, polarizing optical microscopy (POM), conductivity measurements, and small angle neutron scattering (SANS). Three concentration regimes are examined: A dilute regime (with concentrations [CTAB] < 5 wt %) consisting of noninteracting spherical micelles, a semidilute regime (5 wt % ? [CTAB] ? 45 wt %) where micelles interact via electrostatic repulsions, and a concentrated regime (45 wt % < [CTAB] ? 62 wt %) where a reversible, temperature-dependent isotropic (L(1)) to hexatic (Hex) phase transition is observed. The L(1)-Hex transition, which has been predicted but not previously observed, is characterized by (1) a sharp increase in the shear viscosity, (2) the formation of focal conical birefringence textures (observed by POM), and (3) enhancement of the crystalline order, evidenced by the appearance of Bragg reflections in the SANS profiles. Ionic conductivity is not sensitive to the L(1)-Hex transition, which corroborates the absence of topological transitions. PMID:22877559

  19. 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.

  20. Acoustic Desorption from a Room Temperature Ionic Liquid.

    NASA Astrophysics Data System (ADS)

    Harris, Peter; Tracy, Eugene; Cooke, William

    2007-06-01

    We use laser induced acoustic pulses to efficiently desorb ions from a Room Temperature Ionic Liquid (RTIL) in vacuum. Our RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate, remains a stable liquid at pressures exceeding 10-9 torr. We use the 2^nd harmonic of a Nd:YAG laser, 2ns pulse time, to generate acoustic pulses via laser ablation of the backside of a metal foil. Both negative and positive ions are desorbed from the liquid RTIL surface on the front side of the foil. The m/q of ejected ions is detected via TOF measurements from an imaging micro-channel plate detector. We measure the time our acoustic pulse reaches the RTIL surface by detecting the ejected electron signal. We present data showing the variation of desorbed ion yield as a function of the amplitude and shape of the incident acoustic pulse.

  1. 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

  2. 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

  3. Mechanism of graphene formation by graphite electro-exfoliation in ionic liquids-water mixtures

    NASA Astrophysics Data System (ADS)

    Xu, Junli; Shi, Zhongning; Zhang, Xia; Haarberg, Geir Martin

    2014-12-01

    Graphene was produced from graphite electrode by exfoliation in ionic liquid. The influences of process parameters such as ionic liquid concentration, electrolysis potential and the type of anions in the ionic liquid on the production of graphene were studied, and a new mechanism is proposed. The results show that the increase of ionic liquid concentration is beneficial for the formation of graphene, and it is easier to produce graphene by increasing the applied voltage. Ionic liquids anions have great effect on the production of graphene. Both graphite anode and graphite cathode can be modified to graphene during electrolysis. Gases formed inside of the electrode play an important role for the production of graphene, while ionic liquids serve to accelerate the switching rate of graphite to graphene.

  4. 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.

  5. Double-layer in ionic liquids: paradigm change?

    PubMed

    Kornyshev, Alexei A

    2007-05-24

    Applications of ionic liquids at electrified interfaces to energy-storage systems, electrowetting devices, or nanojunction gating media cannot proceed without a deep understanding of the structure and properties of the interfacial double layer. This article provides a detailed critique of the present work on this problem. It promotes the point of view that future considerations of ionic liquids should be based on the modern statistical mechanics of dense Coulomb systems, or density-functional theory, rather than classical electrochemical theories which hinge on a dilute-solution approximation. The article will, however, contain more questions than answers. To trigger the discussion, it starts with a simplified original result. A new analytical formula is derived to rationalize the potential dependence of double-layer capacitance at a planar metal-ionic liquid interface. The theory behind it has a mean-field character, based on the Poisson-Boltzmann lattice-gas model, with a modification to account for the finite volume occupied by ions. When the volume of liquid excluded by the ions is taken to be zero (that is, if ions are extremely sparsely packed in the liquid), the expression reduces to the nonlinear Gouy-Chapman law, the canonical result typically used to describe the potential dependence of capacitance in electrochemical double layers. If ionic volume exclusion takes more realistic values, the formula shows that capacitance-potential curves for an ionic liquid may differ dramatically from the Gouy-Chapman law. Capacitance has a maximum close to the potential of zero charge, rather than the familiar minimum. At large potenials, capacitance decreases with the square root of potential, rather than increases exponentially. The reported formula does not take into account the specific adsorption of ions, which, if present, can complicate the analysis of experimental data. Since electrochemists use to think about the capacitance data in terms of the classical Gouy-Chapman theory, which, as we know, should be good only for electrolytes of moderate concentration, the question of which result is "better" arises. Experimental data are sparse, but a quick look at them suggests that the new formula seems to be closer to reality. Opinions here could, however, split. Indeed, a comparison with Monte Carlo simulations has shown that incorporation of restricted-volume effects in the mean-field theory of electrolyte solutions may give results that are worse than the simple Gouy-Chapman theory. Generally, should the simple mean-field theory work for such highly concentrated ionic systems, where the so-called ion-correlation effects must be strong? It may not, as it does not incorporate a possibility of charge-density oscillations. Somehow, to answer this question definitely, one should do further work. This could be based on density-functional theory (and possibly not on what is referred to as local density approximation but rather "weighted density approximation"), field theory methods for the account of fluctuations in the calculation of partition function, heuristic integral equation theory extended to the nonlinear response, systematic force-field computer simulations, and, most importantly, experiments with independently determined potentials of zero charge, as discussed in the paper. PMID:17469864

  6. Measurements of the complete solvation response in ionic liquids.

    PubMed

    Arzhantsev, Sergei; Jin, Hui; Baker, Gary A; Maroncelli, Mark

    2007-05-10

    Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4'-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25 degrees C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20%) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids. PMID:17319715

  7. 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.

  8. 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, Risn 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.

  9. 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's free energy data and literature enthalpy data. This study highlights that the hydrophobic interaction persists even in the limit of infinite dilution where the hydration effects are usually dominant, implying importance of hydrophobic hydration. Analysis of the results further shows that the hydration of amino acid ionic liquids occurs through the cooperative H-bond formation with the kosmotropic effect in contrast to the usual inorganic salts or hydrophobic salts like tetraalkylammonium halides. PMID:23293839

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

    NASA Astrophysics Data System (ADS)

    Takeya, J.

    2008-10-01

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

  11. 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 ? 4.6A 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

  12. High current density electrodeposition from silver complex ionic liquids.

    PubMed

    Schaltin, Stijn; Brooks, Neil R; Stappers, Linda; Van Hecke, Kristof; Van Meervelt, Luc; Binnemans, Koen; Fransaer, Jan

    2012-02-01

    Liquid metal salts are electrolytes with the highest possible metal concentration for electrodeposition, because the metal ion is an integral part of the solvent. This paper introduces the new ionic silver complexes [Ag(MeCN)(4)](2)[Ag(Tf(2)N)(3)], [Ag(MeCN)][Tf(2)N] and [Ag(EtIm)(2)][Tf(2)N], where MeCN stands for acetonitrile, EtIm for 1-ethylimidazole and Tf(2)N is bis(trifluoromethylsulfonyl)imide. These complexes have been characterized by differential scanning calorimetry, single crystal X-ray crystallography, thermogravimetrical analysis, Raman spectroscopy and cyclic voltammetry. [Ag(MeCN)(4)](2)[Ag(Tf(2)N)(3)] is a room temperature ionic liquid. Smooth silver layers of good quality could be deposited from it, at current densities of up to 25 A dm(-2) in unstirred solutions. [Ag(EtIm)(2)][Tf(2)N] melts at 65 C and can be used as an electrolyte for silver deposition above this temperature. [Ag(MeCN)][Tf(2)N] has a melting point that is too high to be useful in electrodeposition. Addition of thiourea or 1H-benzotriazole to the electrolyte decreased the surface roughness of the silver coatings. The morphology of the metal layers was investigated by atomic force microscopy (AFM). Adsorption of 1H-benzotriazole on the silver metal surface has been proven by Raman spectroscopy. This work shows the usefulness of additives in improving the quality of metal films electrodeposited from ionic liquids. PMID:22193991

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

    PubMed

    Elbourne, Aaron; McDonald, Samila; Vochovsky, 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

  14. 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 technologies and electrochemistry. PMID:25000475

  15. 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

  16. Hydrogenation of CO2 to formic acid promoted by a diamine-functionalized ionic liquid.

    PubMed

    Zhang, Zhaofu; Hu, Suqin; Song, Jinliang; Li, Wenjing; Yang, Guanying; Han, Buxing

    2009-01-01

    Amines to an end: The basic diamine-functionalized ionic liquid 1,3-di(N,N-dimethylaminoethyl)-2-methylimidazolium trifluoromethanesulfonate was prepared and used in the hydrogenation of CO(2) to formic acid. One mole of the ionic liquid coordinates two moles of formic acid to promote the reaction. Both the ionic liquid and catalyst can be reused directly after their separation from the formic acid produced. PMID:19266516

  17. 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.

  18. Fluorescence of fullerene C 70 in ionic liquids

    NASA Astrophysics Data System (ADS)

    Martins, Sofia; Fedorov, Aleksander; Afonso, Carlos A. M.; Baleizo, Carlos; Berberan-Santos, Mrio 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.

  19. 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

  20. Weighing the surface charge of an ionic liquid

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03965g

  1. 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 cellulose, filter paper and cottonwere hydrolyzed 2 10 times faster than the respective untreated celluloses. A complete hydrolysis of Avicel cellulose could be achieved in 6 h given the Trichoderma reesei cellulase/substrate ratio (w/w) of 3:20 at 50 C. In addition,we observed that cellulase is more thermally stable (up to 60 C) in the presence of regenerated cellulose. Furthermore, our systematic studies suggest that the presence of various ILs during the hydrolysis induced different degrees of cellulase inactivation. Therefore, a thorough removal of IL residues after cellulose regeneration is highly recommended, and a systematic investigation on this subject is much needed.

  2. 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.

  3. The role of ionic liquids in hydrogen storage.

    PubMed

    Sahler, Sebastian; Sturm, Sebastian; Kessler, Michael T; Prechtl, Martin H G

    2014-07-14

    Ionic liquid (IL) based H2 storage for H2 generation from NH3BH3 derivatives is shown. These systems promote H2 generation at low temperature, with good reaction rates and high total H2 yields. The effects of ILs and the H2 yield in correlation with the basicity, the cations of the ILs, and the role of carbenes are discussed. Furthermore, mechanistic findings on the dehydrogenation are described. IL material blends are competitive with conventional H2 storage materials with experimental efficiencies of at least 6.5?wt?% H2. PMID:24954029

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

    PubMed

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

    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 10wt% 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 non-volatile 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. approximately 70 degrees 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((R)) cellulose, filter paper and cotton were hydrolyzed 2-10 times faster than the respective untreated celluloses. A complete hydrolysis of Avicel((R)) cellulose could be achieved in 6h given the Trichoderma reesei cellulase/substrate ratio (w/w) of 3:20 at 50 degrees C. In addition, we observed that cellulase is more thermally stable (up to 60 degrees C) in the presence of regenerated cellulose. Furthermore, our systematic studies suggest that the presence of various ILs during the hydrolysis induced different degrees of cellulase inactivation. Therefore, a thorough removal of IL residues after cellulose regeneration is highly recommended, and a systematic investigation on this subject is much needed. PMID:18822323

  5. Heterogeneous dynamics of ionic liquids from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Habasaki, J.; Ngai, K. L.

    2008-11-01

    Molecular dynamics simulations have been performed to study the complex and heterogeneous dynamics of ions in ionic liquids. The dynamics of cations and anions in 1-ethyl-3-methyl imidazolium nitrate (EMIM-NO3) are characterized by van Hove functions and the corresponding intermediate scattering functions Fs(k,t) and elucidated by the trajectories augmented by the use of singular spectrum analysis (SSA). Several time regions are found in the mean squared displacement of the ions. Change in the slope in a plot of the diffusion coefficient against temperature is found at around 410K in the simulation. Heterogeneous dynamics with the presence of both localized ions and fast ions capable of successive jumps were observed at long time scales in the self-part of the van Hove functions and in the trajectories. Non-Gaussian dynamics are evidenced by the self-part of the van Hove functions and wave number dependence of Fs(k,t) and characterized as Lvy flights. Successive motion of some ions can continue even after several nanoseconds at 370K, which is longer than the onset time of diffusive motion, tdif. Structure of the long time dynamics of fast ions is clarified by the phase space plot of the successive motion using the denoised data by SSA. The continual dynamics are shown to have a long term memory, and therefore local structure is not enough to explain the heterogeneity. The motion connecting localized regions at about 370K is jumplike, but there is no typical one due to local structural changes during jump motion. With the local motion, mutual diffusion between cation and anion occurs. On decreasing temperature, mutual diffusion is suppressed, which results in slowing down of the dynamics. This "mixing effect of cation and anion" is compared with the "mixed alkali effect" found in the ionics in the ionically conducting glasses, where the interception of paths by different alkali metal ions causes the large reduction in the dynamics [J. Habasaki and K. L. Ngai, Phys. Chem. Chem. Phys. 9, 4673 (2007), and references herein]. Although a similar mechanism of the slowing down is observed, strong coupling of the motion of cation and anion prevents complete interception unless deeply supercooled, and this explains the wide temperature region of the existence of the liquid and supercooled liquid states in the ionic liquid.

  6. Microslips to "Avalanches" in Confined, Molecular Layers of Ionic Liquids.

    PubMed

    Espinosa-Marzal, R M; Arcifa, A; Rossi, A; Spencer, N D

    2014-01-01

    We have measured forces between mica surfaces across two hydrophobic ionic liquids with a surface forces apparatus. Both surface-adsorbed water and alkyl-chain length on the imidazolium cation influence the structure of the nanoconfined film and the dynamics of film-thickness transitions. Friction shows accumulative microslips as precursors to collective "avalanches" that abruptly reduce friction momentarily. This behavior is interpreted as a consequence of interlayer ion correlations within the 1 to 2 nm thick film; we identify this to be analogous to the friction response of crackling noise systems over a broad range of sizes. PMID:26276199

  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. 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

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

    DOEpatents

    Pagoria, Philip (Livermore, CA); Maiti, Amitesh (San Ramon, CA); Gash, Alexander (Brentwood, CA); Han, Thomas Yong (Pleasanton, CA); Orme, Christine (Oakland, CA); Fried, Laurence (Livermore, CA)

    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.

  10. Carboxyl-functionalized task-specific ionic liquids for solubilizing metal oxides.

    PubMed

    Nockemann, Peter; Thijs, Ben; Parac-Vogt, Tatjana N; Van Hecke, Kristof; Van Meervelt, Luc; Tinant, Bernard; Hartenbach, Ingo; Schleid, Thomas; Ngan, Vu Thi; Nguyen, Minh Tho; Binnemans, Koen

    2008-11-01

    Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethylsulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior has been investigated by (1)H NMR, and it was found that it can be attributed to the temperature-dependent hydration and hydrogen-bond formation of the ionic liquid components. The crystal structures of four ionic liquids and five metal complexes have been determined. PMID:18841931

  11. 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 properties that must be optimized to enable ionic liquids to be cost-competitive for CO{sub 2} capture. It was found that increasing the capacity of the ionic liquids for CO{sub 2} would be important, and that doing so could potentially make ionic liquids more effective than conventional amine solvents.

  12. Ionic liquids as heat transfer fluids: comparison with known systems, possible applications, advantages and disadvantages

    NASA Astrophysics Data System (ADS)

    Chernikova, E. A.; Glukhov, L. M.; Krasovskiy, V. G.; Kustov, L. M.; Vorobyeva, M. G.; Koroteev, A. A.

    2015-08-01

    The practical aspects and prospects of application of ionic liquids as heat transfer fluids are discussed. The physicochemical properties of ionic liquids (heat capacity, thermal conductivity, thermal and radiation stability, viscosity, density, saturated vapour pressure and corrosion activity) are compared with the properties of some commercial heat transfer fluids. The issues of toxicity of ionic liquids are considered. Much attention is paid to known organosilicon heat transfer fluids, which are considered to have much in common with ionic liquids in the set of properties and are used in the review as reference materials. The bibliography includes 132 references.

  13. 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.

  14. 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.

  15. Dipolar motions and ionic conduction in an ibuprofen derived ionic liquid.

    PubMed

    Viciosa, M T; Santos, G; Costa, A; Danède, F; Branco, L C; Jordão, N; Correia, N T; Dionísio, M

    2015-10-01

    It was demonstrated that the combination of the almost water insoluble active pharmaceutical ingredient (API) ibuprofen with the biocompatible 1-ethanol-3-methylimidazolium [C2OHMIM] cation of an ionic liquid (IL) leads to a highly water miscible IL-API with a solubility increased by around 5 orders of magnitude. Its phase transformations, as crystallization and glass transition, are highly sensitive to the water content, the latter shifting to higher temperatures upon dehydration. By dielectric relaxation spectroscopy the dynamical behavior of anhydrous [C2OHMIM][Ibu] and with 18.5 and 3% of water content (w/w) was probed from well below the calorimetric glass transition (Tg) up to the liquid state. Multiple reorientational dipolar processes were detected which become strongly affected by conductivity and electrode polarization near above Tg. Therefore [C2OHMIM][Ibu] exhibits mixed behavior of a conventional molecular glass former and an ionic conductor being analysed in this work through conductivity, electrical modulus and complex permittivity. The dominant process, σα-process, originates by a coupling between both charge transport and dipolar mechanisms. The structural relaxation times were derived from permittivity analysis and confirmed by temperature modulated differential scanning calorimetry. The temperature dependence of the β-secondary relaxation is coherent with a Johari-Goldstein (βJG) process as detected in conventional glass formers. PMID:26315452

  16. 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

  17. Ionic liquids as solvents for in situ dispersive liquid-liquid microextraction of DNA.

    PubMed

    Li, Tianhao; Joshi, Manishkumar D; Ronning, Donald R; Anderson, Jared L

    2013-01-11

    Six ionic liquids (ILs) were applied for the first time as solvents in the extraction and preconcentration of deoxyribonucleic acid (DNA) using an in situ dispersive liquid-liquid microextraction (DLLME) approach. The effect of different IL substituents and functional group on the extraction efficiency of DNA was investigated. The highest extraction efficiencies of DNA were obtained using 1-(1,2-dihydroxypropyl)-3-hexadecylimidazolium bromide (C(16)POHIM-Br) and N,N-didecyl-N-methyl-d-glucaminium bromide [(C(10))(2)NMDG-Br]. Extraction efficiencies higher than 97% were obtained using small amounts of IL (0.50mg) for each extraction. The extraction of DNA from a sample matrix containing metal ions and protein revealed that the metal ions did not interfere with the extraction of DNA and that the co-extraction of protein can be mitigated by performing the extraction under moderately acidic conditions. Data from (31)P NMR spectroscopy suggest that a combination of electrostatic and ?-? interactions dominate IL-DNA complexation and that the extraction is concentration dependant. PMID:23261290

  18. Exploring field effects on ionic liquid boundary lubrication

    NASA Astrophysics Data System (ADS)

    Capozza, Rosario; Benassi, Andrea; Vanossi, Andrea; Tosatti, Erio

    2014-03-01

    Ionic liquids, organic salts that are liquid at room temperature, are of great physical as well as of technological interest. Their adhesion properties to solid surfaces under pressure suggests their use as boundary lubricants. One potentially interesting feature would be the possibility that electrical charging of the solid plates or more generally an applied static or dynamic electric field could modify the nearby perpendicular and parallel ordering of ions, and in turn also modify the sliding friction. While these effects have just begun to be pursued by experimental groups, we have undertaken molecular dynamics simulations aimed at exploring some of these questions. Preliminary results obtained using very simple molten salt boundary lubrication models will be presented and discussed. Partly sponsored by SNSF Project CRSII2 136287/1, and by ERC Grant N. 320796 MODPHYSFRICT.

  19. Interfacial phase transitions in imidazolium-based ionic liquids

    NASA Astrophysics Data System (ADS)

    Halka, V.; Tsekov, R.; Freyland, W.

    2005-11-01

    We report measurements of the surface tension and capillary wave spectra at the liquid/vapour interface of the ionic liquids [C4mim]+X- (X- = Cl-,AlCl4-) and compare these with recent results of [C4mim]+PF6-. Special attention is given to the temperature dependence of the surface dipole moment density ?(T), which has been derived from the capillary wave spectra with the aid of the properly extended dispersion relation. For [C4mim]+PF6- an order-disorder interfacial phase transition with a critical temperature of Tc = 385 K is found, which has not been reported before. At higher temperatures a first order ferroelectric surface phase transition is indicated in ?(T) of both [C4mim]+PF6- and [C4mim]+Cl- melts. Increasing the anion size in [C4mim]+AlCl4-, these interfacial phase transitions are suppressed.

  20. On the formation of a protic ionic liquid in nature.

    PubMed

    Chen, Li; Mullen, Genevieve E; Le Roch, Myriam; Cassity, Cody G; Gouault, Nicolas; Fadamiro, Henry Y; Barletta, Robert E; O'Brien, Richard A; Sykora, Richard E; Stenson, Alexandra C; West, Kevin N; Horne, Howard E; Hendrich, Jeffrey M; Xiang, Kang Rui; Davis, James H

    2014-10-27

    The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S.?invicta and N.?fulva. After being sprayed with alkaloid-based S.?invicta venom, N.?fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S.?invicta venom alkaloids. The resulting mixed-cation ammonium formate milieu has properties consistent with its classification as a protic IL. PMID:25045040

  1. 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.

  2. Photochromic imidazolium based ionic liquids based on spiropyran.

    PubMed

    Coleman, Simon; Byrne, Robert; Alhashimy, Nameer; Fraser, Kevin J; Macfarlane, Douglas R; Diamond, Dermot

    2010-07-14

    We investigate the physicochemical properties of a novel imidazolium benzospiropyran derivative, SP(Im), in imidazolium based ionic liquids (ILs). SP(Im) was prepared through alkylation of an imidazole to the photoswitchable compound and this derivative was characterised in imidazolium based ILs with increasing chain length to examine the stability of its merocyanine (MC) and spiropyran (SP) forms and compared to standard spiropyran, BSP. The rate of thermal relaxation of the new derivative is found to be about ten times faster than that of BSP as reflected in rates of 13.9 x 10(-3) s(-1) and 1.0 x 10(-3) s(-1) for SP(Im) and BSP, respectively, in [C(6)mIm][NTf(2)]. Since ILs are believed to form nano-structured domains it is proposed that the covalent attachment of the imidazolium side group of SP(Im) fully integrates the photoswitchable moiety into the non-polar region through side-chain association. In contrast, unbound BSP is relatively free to migrate between both polar and non-polar regions and the MC form is more readily stabilised by the IL charge via through space interactions and spontaneous movement to charged nano-domains leading to enhancement of the MC lifetime. At higher concentrations, rheological and transport properties were investigated to determine the impact of covalent attachment of the BSP fragment to an imidazolium cation on the ionic liquid structure. Ionic conductivity was found to decrease by up to 23% for SP(Im) with effects increasing with cation side-chain length. Unlike BSP, the photoswitching of the SP(Im) did not affect conductivity or viscosity values. This may indicate that the mobility of the photoswitchable compound and the resulting disruption of such movement may be critical to the control of this physical property. PMID:20467657

  3. Rationale for the implementation of reference electrodes in ionic liquids.

    PubMed

    Bonnaud, C; Billard, I; Papaiconomou, N; Chainet, E; Leprtre, J C

    2016-03-01

    A thorough investigation of the reference electrodes for electrochemical measurements is presented in three ionic liquids (ILs), namely 1-butyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide [BMIM][Tf2N], 1-octyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide [OMIM][Tf2N] and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide [BMPyrr][Tf2N]. The influence of technical aspects such as internal resistance, scan rate and concentration of the active species on cyclic voltammetry has been investigated using three quasi-reference electrodes (QREs) (AgCl, Pt, and Pd) and three reference electrodes (REs) (Fc(+)/Fc/Pt, Ag(+)/Ag, and Cl(-)/AgCl/Ag). The results show that the internal resistance has to be taken dynamically into account during any cyclic voltammetry experiment. Quasi-reference electrodes can be used only for qualitative electrochemical studies. Reference electrodes based on Ag(+)/Ag or Fc(+)/Fc dissolved in an IL have a stable potential over 15 h and thus can be used to perform reliable electrochemical experiments in ionic liquids and to get quantitative information such as potentials. PMID:26924558

  4. Two phosphonium ionic liquids with high Li(+) transport number.

    PubMed

    Martins, Vitor L; Sanchez-Ramirez, Ndher; Ribeiro, Mauro C C; Torresi, Roberto M

    2015-09-21

    This work presents the physicochemical characterization of two ionic liquids (ILs) with small phosphonium cations, triethylpenthylphosphonium bis(trifluoromethanesulfonyl)imide ([P2225][Tf2N]) and (2-methoxyethyl)trimethylphosphonium bis(trifluoromethanesulfonyl)imide ([P222(201)][Tf2N]), and their mixtures with Li(+). Properties such as the electrochemical window, density, viscosity and ionic conductivity are presented. The diffusion coefficient was obtained using two different techniques, PGSE-NMR and Li electrodeposition with microelectrodes. In addition, the Li(+) transport number was calculated using the PGSE-NMR technique and an electrochemical approach. The use of these three techniques showed that the PGSE-NMR technique underestimates the diffusion coefficient for charged species. The Li(+) transport number was found to be as high as 0.54. Raman spectroscopy and molecular dynamics simulations were used to evaluate the short-range structure of the liquids. These experiments suggested that the interaction between the Li(+) and the Tf2N(-) anion is similar to that seen with other ILs containing the same anion. However, the MD simulations also showed that the Li(+) ions interact differently with the cation containing an alkyl ether chain. The results found in this work suggest that these Li(+) mixtures have promising potential to be applied as electrolytes in batteries. PMID:26272339

  5. Dialkylimidazolium ionic liquids hydrolyze cellulose under mild conditions.

    PubMed

    Gazit, Oz M; Katz, Alexander

    2012-08-01

    The average molecular weight of cellulose derived from filter paper, poplar, and Avicel decreases by up to two orders of magnitude during typical mild dissolution protocols using ionic liquids (ILs). About an order of magnitude greater cellulose depolymerization rate during ionic liquid dissolution occurs in 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-ethyl-3-methylimidazolium chloride (EmimCl) compared to 1-ethyl-3-methylimidazolium acetate (EmimOAc), and, unintuitively, greater IL purity results in greater cellulose depolymerization. The following data support the mechanism of cellulose hydrolysis to be acid-catalyzed: (i) increase in number of reducing ends following cellulose dissolution in IL; (ii) addition of N-methylimidazolium base suppresses cellulose depolymerization during dissolution in IL; (iii) small amounts of glucose and traces of hydroxymethyl furfural are present following cellulose dissolution in IL. The acid is presumably synthesized via IL decomposition to generate a carbene and proton, consistent with hypothesis derived from molecular modeling. Titration experiments conducted here measure the amount of acid synthesized to be in the 4000 ppm range for high-purity BmimCl IL during mild processing conditions for cellulose dissolution. This data is relevant for understanding the extent of IL decomposition during biomass dissolution. PMID:22550059

  6. (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

  7. 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

  8. 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

  9. Antitumor Activity of Ionic Liquids Based on Ampicillin.

    PubMed

    Ferraz, Ricardo; Costa-Rodrigues, Joo; Fernandes, Maria H; Santos, Miguel M; Marrucho, Isabel M; Rebelo, Lus Paulo N; Prudncio, Cristina; Noronha, Joo Paulo; Petrovski, eljko; Branco, Lus 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

  10. 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.

  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. 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].

  13. 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.

  14. 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.

  15. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    The electrical conductivity of room temperature ionic liquid (IL) is investigated with molecular dynamics simulation. A trajectory of 1 ?s 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.

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

  18. 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.

  19. Performance evaluation of supported ionic liquid membrane for removal of phenol.

    PubMed

    Nosrati, S; Jayakumar, N S; Hashim, M A

    2011-09-15

    This work evaluates the performance of ionic liquid in supported liquid membrane (SLM) for the removal of phenol from wastewater. Ionic liquids are organic salts entirely composed of organic cations and either organic or inorganic anions. Due to the fact that the vapor pressure of ionic liquid is not detectable and they are sparingly soluble in most conventional solvents, they can be applied in SLM as the organic phase. In this work, 1-n-alkyl-3-methylimidazolium salts, [C(n)MIM](+)[X](-) have been investigated so as to determine an optimal supported ionic liquid membrane. The effect of operational parameters such as pH, stirring speed and the concentration of stripping agent has been studied, and an evaluation of different membrane supports were also carried out. With a minimal amount of the ionic liquid 1-Butyl-3-methylimidazolium hydrogensulfate, 85% phenol removal could be achieved by using polytetrafluoroethylene hydrophobic membrane filter in the SLM. PMID:21752542

  20. Nano-biphasic ionic liquid systems composed of hydrophobic phosphonium salts and a hydrophilic ammonium salt.

    PubMed

    Taguchi, Satomi; Ichikawa, Takahiro; Kato, Takashi; Ohno, Hiroyuki

    2012-05-28

    A combination of a phosphonium-type-zwitterions-lithium bis(trifluoromethanesulfonyl)imide complex and a hydrophilic ammonium salt provides a nanosegregated liquid-crystalline matrix consisting of hydrophilic ionic liquid (IL) domains and hydrophobic IL domains. PMID:22510870

  1. Solvation and rotational dynamics of coumarin 153 in ionic liquids: comparisons to conventional solvents.

    PubMed

    Jin, Hui; Baker, Gary A; Arzhantsev, Sergei; Dong, Jing; Maroncelli, Mark

    2007-06-28

    Steady-state and time-resolved emission spectroscopy with 25 ps resolution are used to measure equilibrium and dynamic aspects of the solvation of coumarin 153 (C153) in a diverse collection of 21 room-temperature ionic liquids. The ionic liquids studied here include several phosphonium and imidazolium liquids previously reported as well as 12 new ionic liquids that incorporate two homologous series of ammonium and pyrrolidinium cations. Steady-state absorption and emission spectra are used to extract solvation free energies and reorganization energies associated with the S0 <--> S1 transition of C153. These quantities, especially the solvation free energy, vary relatively little in ionic liquids compared to conventional solvents. Some correlation is found between these quantities and the mean separation between ions (or molar volume). Time-resolved anisotropies are used to observe solute rotation. Rotation times measured in ionic liquids correlate with solvent viscosity in much the same way that they do in conventional polar solvents. No special frictional coupling between the C153 and the ionic liquid solvents is indicated by these times. But, in contrast to what is observed in most low-viscosity conventional solvents, rotational correlation functions in ionic liquids are nonexponential. Time-resolved Stokes shift measurements are used to characterize solvation dynamics. The solvation response functions in ionic liquids are also nonexponential and can be reasonably represented by stretched-exponential functions of time. The solvation times observed are correlated with the solvent viscosity, and the much slower solvation in ionic liquids compared to dipolar solvents can be attributed to their much larger viscosities. Solvation times of the majority of ionic liquids studied appear to follow a single correlation with solvent viscosity. Only liquids incorporating the largest phosphonium cation appear to follow a distinctly different correlation. PMID:17530885

  2. Suspension Array of Ionic Liquid or Ionic Liquid-Quantum Dots Conjugates for the Discrimination of Proteins and Bacteria.

    PubMed

    Chen, Shuai; Wei, Ling; Chen, Xu-Wei; Wang, Jian-Hua

    2015-11-01

    It is of great importance to develop novel and sensitive sensing materials for the detection of proteins and microorganisms to fulfill the demand of disease diagnosis. As the selectivity and sensitivity of sensing systems are highly dependent on the receptor, the fluorescent sensor array with imidazolium ionic liquids (ILs) and ionic liquid-quantum dots conjugates as semiselective receptors is developed for protein/bacteria differential sensing or discrimination. The IL sensing system formed by 1,3-dibutylimidazolium chloride (BBimCl), 1,3-diethylimidazolium bromine (EEimBr), 1,3-dibutylimidazolium bromine (BBimBr), 1,3-dihexylimidazolium bromine (HHimBr), and 1,3-dioctylimidazolium bromine (OOimBr) and the IL@QDs/QDs sensing system formed by CdTe, BBimCl@CdTe, EEimBr@CdTe, BBimBr@CdTe, and HHimBr@CdTe are tested, by transferring the interaction binding difference between receptors and proteins to the fluorescent response pattern. The IL sensing system is applied to the identification of 48 samples (8 proteins at 500 nM) with an accuracy of 91.7%. For the IL@QDs/QDs sensing system, 8 proteins are completely distinguished with 100% accuracy at a very low concentration level of 10 nM. Remarkably, 36 training cases (6 strains of bacteria from 3 different species) are discriminated with 100% (OD600 of 0.1). PMID:26424154

  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. Enhanced electrical transport in ionic liquid dispersed TMAI-PEO solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Gupta, Neha; Rathore, Munesh; Dalvi, Anshuman; Kumar, Anil

    2014-04-01

    A polymer composite is prepared by dispersing ionic liquid [Bmim][BF4] 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 × 10-5 for 10 wt % ionic liquid.

  6. Lyotropic liquid crystal phases of phytantriol in a protic ionic liquid with fluorous anion.

    PubMed

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

    2014-10-21

    The phase behaviour of phytantriol in the protic ionic liquid (PIL) 1-methylimidazolium pentadecafluorooctanoate (MImOF) and four different MImOF-water compositions was investigated by small- and wide-angle X-ray scattering (SAXS/WAXS), cross polarised optical microscopy (CPOM) and infrared spectroscopy (IR). MImOF is a distinct protic ionic liquid in that it contains a fluorocarbon anion and a hydrocarbon cation. This leads to MImOF having an unusual liquid nanostructure, such that it contains fluorocarbon, hydrocarbon and polar domains. No lyotropic liquid crystal phases were observed for phytantriol in neat MImOF. However, on addition of water, lamellar, cubic Ia3d and micellar phases were observed for specific MImOF-phytantriol-water compositions at room temperature, and up to 60 C. The phase behaviour for phytantriol in the solvent mixture of 25 wt%-MImOF-75 wt%-water was the most similar to the phytantriol-water phase diagram. Only this MImOF-water composition supported the Ia3d cubic phase, which had a lattice parameter between 100-140 compared to 86-100 in deionised water, indicating significant swelling due to the MImOF. IR spectroscopy showed that a percentage of the water molecules were hydrogen bonded to the N-H of the MIm cation, and this water decreased the hydrogen bonding present between the cation and anion of the ionic liquid. This investigation furthers our understanding of the interaction of ionic liquids with solutes, and the important role that the different IL nanostructures can have on influencing these interactions. PMID:25177837

  7. 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-methylimidazolium bis(trifluoromethylsulfonyl)imide. PMID:26771378

  8. NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

    NASA Astrophysics Data System (ADS)

    Kikuchi, Kunitomo; Tsuchitani, Shigeki

    2009-09-01

    Nafion-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

  9. Viscosity Measurements on Ionic Liquids: A Cautionary Tale

    NASA Astrophysics Data System (ADS)

    Diogo, Joo C. F.; Caetano, Fernando J. P.; Fareleira, Joo 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.

  10. 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.

  11. NMR investigation of ionic liquid-LiX mixtures: pyrrolidinium cations and TFSI- anions.

    PubMed

    Nicotera, Isabella; Oliviero, Cesare; Henderson, Wesley A; Appetecchi, Giovanni B; Passerini, Stefano

    2005-12-01

    In this paper is reported an extensive NMR characterization of N-methyl-N-propyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13TFSI) room-temperature ionic liquid and its mixtures with LiTFSI. NMR was used to investigate the interactions between the ionic liquid and lithium salt and the diffusion coefficients of all ionic species present in these mixtures. The results are compared with previous DSC, Raman, and electrochemical investigations. PMID:16853972

  12. 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.

  13. 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 %.

  14. Comparison of three ionic liquid-tolerant cellulases by molecular dynamics.

    PubMed

    Jaeger, Vance; Burney, Patrick; Pfaendtner, Jim

    2015-02-17

    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

  15. 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

  16. Concentration-dependent apparent partition coefficients of ionic liquids possessing ethyl- and bi-sulphate anions.

    PubMed

    Jain, Preeti; Kumar, Anil

    2015-12-23

    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 ?-? 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

  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. Method of purifying a gas stream using 1,2,3-triazolium ionic liquids

    DOEpatents

    Luebke, David; Nulwala, Hunald; Tang, Chau

    2014-12-09

    A method for separating a target gas from a gaseous mixture using 1,2,3-triazolium ionic liquids is presented. Industrial effluent streams may be cleaned by removing carbon dioxide from the stream by contacting the effluent stream with a 1,2,3-triazolium ionic liquid compound.

  19. 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

    2016-01-26

    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

  20. Enthalpies of dissolution of ionic liquids in water-acetonitrile solutions at 298.15 K

    NASA Astrophysics Data System (ADS)

    Belov, A. V.; Solov'ev, S. N.

    2015-02-01

    Enthalpies of dissolution of ionic liquids [C4mim]OTf, [C4mim]NTf2, and [C4mpy]NTf2 are measured in studying the thermodynamic characteristics of solvation and ion association for ionic liquids in nonaqueous and mixed solvents in acetonitrile-water of three compositions at 298.15 K. Standard enthalpies of solution are determined.

  1. Comparison of Dilute Acid and Ionic Liquid Pretreatment of Switchgrass: Biomass Recalcitrance, Delignification and Enzymatic Saccharification

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The efficiency of two biomass pretreatment technologies, dilute acid hydrolysis and dissolution in an ionic liquid, are compared in terms of delignification, saccharification efficiency and saccharide yields with switchgrass serving as a model bioenergy crop. When subject to ionic liquid pretreatme...

  2. 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...

  3. 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...

  4. Morphology, Modulus, and Ionic Conductivity of a Triblock Terpolymer/Ionic Liquid Electrolyte Membrane

    NASA Astrophysics Data System (ADS)

    McIntosh, Lucas D.; Lodge, Timothy P.

    2013-03-01

    A key challenge in designing solid polymer electrolytes is increasing bulk mechanical properties such as stiffness, without sacrificing ionic conductivity. Previous work has focused on diblock copolymers, where one block is a stiff, glassy insulator and the other is a flexible ion conductor. Disadvantages of these systems include difficulty in achieving network morphologies, which minimize dead-ends for ion transport, and the necessity to operate below both the Tg of the glassy block and the order-disorder temperature. We have investigated the triblock terpolymer poly[isoprene-b-(styrene-co-norbornenylethyl styrene)-b-ethylene oxide] because it self-assembles into a triply-continuous network structure. SAXS and TEM revealed the bulk morphology of INSO to be disordered but strongly correlated after solvent casting from dichloromethane. This apparent disordered network structure was retained after chemical crosslinking and addition of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide. Impedance spectroscopy confirmed the expected conductivity for ions confined to continuous PEO channels. The mechanical response before and after crosslinking showed an increase in the material modulus.

  5. Ionic liquid based electrolytes for sodium-ion batteries: Na+ solvation and ionic conductivity

    NASA Astrophysics Data System (ADS)

    Monti, Damien; Jnsson, Erlendur; Palacn, M. Rosa; Johansson, Patrik

    2014-01-01

    Ionic liquid (IL) based sodium-ion (Na+) battery electrolytes obtained by mixing imidazolium-TFSI ILs (EMIm-TFSI and BMIm-TFSI) with the corresponding sodium salt (NaTFSI) have been investigated using a wide range of characterization techniques: dielectric spectroscopy, differential scanning calorimetry, densitometry, viscometry, and Raman spectroscopy. The sodium ion conducting electrolytes exhibit excellent ionic conductivities, up to 5.5 mS cm-1 at room temperature, and a useful thermal window of -86 C to 150 C. In more detail, Raman data analysis supported by DFT calculations on Na+-TFSI complexes, allow us to determine the sodium ion solvation and charge carrier nature as a function of salt concentration. The results are compared to data for the corresponding Li systems and while such electrolytes essentially form [Li(TFSI)2]- as the main Li+ carrier, the sodium systems seem to dominantly form [Na(TFSI)3]2- complexes. The effects on conductivity and viscosity and the consequences for sodium-ion battery implementation are discussed.

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

    SciTech Connect

    Wishart, J.F.

    2011-06-12

    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 generally have low volatilities and are combustion-resistant, 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 primary radiation chemistry, 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 reactions and product distributions. We study these issues by characterization of primary radiolysis products and measurements of their yields and reactivity, quantification of electron solvation dynamics and scavenging of electrons in different states of solvation. From this knowledge we wish to learn how to predict radiolytic mechanisms and control them or mitigate their effects on the properties of materials used in nuclear fuel processing, for example, and to apply IL radiation chemistry to answer questions about general chemical reactivity in ionic liquids that will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that the slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increase the importance of pre-solvated electron reactivity and consequently alter product distributions and subsequent chemistry. This difference from conventional solvents has profound effects on predicting and controlling radiolytic yields, which need to be quantified for the successful use under radiolytic conditions. Electron solvation dynamics in ILs are measured directly when possible and estimated using proxies (e.g. coumarin-153 dynamic emission Stokes shifts or benzophenone anion solvation) in other cases. Electron reactivity is measured using ultrafast kinetics techniques for comparison with the solvation process.

  7. Nonhumidified intermediate temperature fuel cells using protic ionic liquids.

    PubMed

    Lee, Seung-Yul; Ogawa, Atsushi; Kanno, Michihiro; Nakamoto, Hirofumi; Yasuda, Tomohiro; Watanabe, Masayoshi

    2010-07-21

    In this paper, the characterization of a protic ionic liquid, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]), as a proton conductor for a fuel cell and the fabrication of a membrane-type fuel cell system using [dema][TfO] under nonhumidified conditions at intermediate temperatures are described in detail. In terms of physicochemical and electrochemical properties, [dema][TfO] exhibits high activity for fuel cell electrode reactions (i.e., the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR)) at a Pt electrode, and the open circuit voltage (OCV) of a liquid fuel cell is 1.03 V at 150 degrees C, as has reported in ref 27. However, diethylmethylammonium bis(trifluoromethane sulfonyl)amide ([dema][NTf(2)]) has relatively low HOR and ORR activity, and thus, the OCV is ca. 0.7 V, although [dema][NTf(2)] and [dema][TfO] have an identical cation ([dema]) and similar thermal and bulk-transport properties. Proton conduction occurs mainly via the vehicle mechanism in [dema][TfO] and the proton transference number (t(+)) is 0.5-0.6. This relatively low t(+) appears to be more disadvantageous for a proton conductor than for other electrolytes such as hydrated sulfonated polymer electrolyte membranes (t(+) = 1.0). However, fast proton-exchange reactions occur between ammonium cations and amines in a model compound. This indicates that the proton-exchange mechanism contributes to the fuel cell system under operation, where deprotonated amines are continuously generated by the cathodic reaction, and that polarization of the cell is avoided. Six-membered sulfonated polyimides in the diethylmethylammonium form exhibit excellent compatibility with [dema][TfO]. The composite membranes can be obtained up to a [dema][TfO] content of 80 wt % and exhibit good thermal stability, high ionic conductivity, and mechanical strength and gas permeation comparable to those of hydrated Nafion. H(2)/O(2) fuel cells prepared using the composite membranes can successfully operate at temperatures from 30 to 140 degrees C under nonhumidified conditions, and a current density of 250 mA cm(-2) is achieved at 120 degrees C. The protic ionic liquid and its composite membrane are a possible candidate for an electrolyte of a H(2)/O(2) fuel cell that operates under nonhumidified conditions. PMID:20578771

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

    PubMed

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

    2015-01-01

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

  9. Contracting cardiomyocytes in hydrophobic room-temperature ionic liquid

    SciTech Connect

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

    2012-10-19

    Highlights: Black-Right-Pointing-Pointer Biocompatible room-temperature ionic liquid was applied on beating cardiomyocyte. Black-Right-Pointing-Pointer The lifetime of beating cardiomyocytes was depended on anion functional group. Black-Right-Pointing-Pointer A longer lifetime was recorded for no functional group on alkyl chain on their anion. Black-Right-Pointing-Pointer Amino group on alkyl chain and fluorine in anion induced fatal condition changes. Black-Right-Pointing-Pointer We reported liquid electrolyte interface to stimulate cardiomyocytes. -- Abstract: Room-temperature ionic liquids (RTILs) are drawing attention as a new class of nonaqueous solvents to replace organic and aqueous solvents for chemical processes in the liquid phase at room temperature. The RTILs are notable for their characteristics of nonvolatility, extremely low vapor pressure, electric conductivity, and incombustibility. These distinguished properties of RTILs have brought attention to them in applications with biological cells and tissue in vacuum environment for scanning electron microscopy, and in microfluidic devices for micro-total analysis system (micro-TAS). Habitable RTILs could increase capability of nonaqueous micro-TAS for living cells. Some RTILs seemed to have the capability to replace water in biological applications. However, these RTILs had been applied to just supplemental additives for biocompatible test, to fixed cells as a substitute for an aqueous solution, and to simple molecules. None of RTILs in which directly soaks a living cell culture. Therefore, we demonstrated the design of RTILs for a living cell culture and a liquid electrolyte to stimulate contracting cardiomyocytes using the RTILs. We assessed the effect of RTILs on the cardiomyocytes using the beating lifetime to compare the applicability of RTILs for biological applications. Frequent spontaneous contractions of cardiomyocytes were confirmed in amino acid anion RTILs [P{sub 8,8,8,8}][Leu] and [P{sub 8,8,8,8}][Ala], phosphoric acid derivatives [P{sub 8,8,8,8}][MeO(H)PO{sub 2}], and [P{sub 8,8,8,8}][C{sub 7}CO{sub 2}]. The anion type of RTILs had influence on applicable characteristics for the contracting cardiomyocyte. This result suggested the possibility for biocompatible design of hydrophobic group RTILs to achieve biological applications with living cells.

  10. Discovering less toxic ionic liquids by using the Microtox toxicity test.

    PubMed

    Hernndez-Fernndez, F J; Bayo, J; Prez de los Ros, A; Vicente, M A; Bernal, F J; Quesada-Medina, J

    2015-06-01

    New Microtox toxicity data of 16 ionic liquids of different cationic and anionic composition were determined. The ionic liquids 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, [BMPyr(+)][TFO(-)], 1-butyl-1-methylpyrrolidinium chloride, [BMPyr(+)][Cl(-)], hydroxypropylmethylimidazolium fluoroacetate, [HOPMIM(+)][FCH2COO(-)], and hydroxypropylmethylimidazolium glycolate [HOPMIM(+)][glycolate(-)] were found to be less toxic than conventional organic solvent such as chloroform or toluene, accoding the Microtox toxicity assays. The toxicity of pyrrolidinium cation was lower than the imidazolium and pyridinium ones. It was found that the inclusion of an hydroxyl group in the alkyl chain length of the cation also reduce the toxicity of the ionic liquid. To sum up, the Microtox toxicity assays can be used as screening tool to easily determined the toxicity of a wide range of ionic liquids and the toxicity data obtained could allow the obtention of structure-toxicity relationships to design less toxic ionic liquids. PMID:25748519

  11. The configuration exchanging theory for transport properties and glass formation temperature of ionic liquids.

    PubMed

    Hu, Yu-Feng; Zhang, Xian-Ming; Qi, Jian-Guang; Yin, Liu-Yi

    2015-11-28

    Understanding molecular motion in terms of molecular structure is an important issue for microscopic understanding of the nature of transport properties and glass transition, and for design of structured materials to meet specific demands in various applications. Herein, a novel molecular mechanism is proposed to connect macroscopic motion in ionic liquids with molecular structure via conformational conversions of the constituent ions or of the cation-anion pairs. New equations for description of relaxation time, diffusion coefficient, molar conductivity, and viscosity of ionic liquids are established. The equation parameters, which were determined from the temperature dependent heat capacities, self-diffusion coefficients, molar conductivities, and viscosities of typical ionic liquids, were used to produce predictions for the corresponding properties of other ionic liquids and for the glass transition temperatures of representative ionic liquids. All predictions are in nice agreements with the experimental results. PMID:26627962

  12. Effect of ionic liquid on activity, stability, and structure of enzymes: a review.

    PubMed

    Naushad, Mu; Alothman, Zied Abdullah; Khan, Abbul Bashar; Ali, Maroof

    2012-11-01

    Ionic liquids have shown their potential as a solvent media for many enzymatic reactions as well as protein preservation, because of their unusual characteristics. It is also observed that change in cation or anion alters the physiochemical properties of the ionic liquids, which in turn influence the enzymatic reactions by altering the structure, activity, enatioselectivity, and stability of the enzymes. Thus, it is utmost need of the researchers to have full understanding of these influences created by ionic liquids before choosing or developing an ionic liquid to serve as solvent media for enzymatic reaction or protein preservation. So, in the present review, we try to shed light on effects of ionic liquids chemistry on structure, stability, and activity of enzymes, which will be helpful for the researchers in various biocatalytic applications. PMID:22732130

  13. Shape selectivity using ionic liquids for the preparation of silver and silver sulphide nanomaterials.

    PubMed

    Patil, Amol B; Bhanage, Bhalchandra M

    2014-02-21

    Electrodeposition of silver and silver sulphide was carried out from two protic ionic liquids. A change of the anion moiety of ionic liquid was found to bring about significant changes in the morphology of the nanocrystalline silver and silver sulphide deposits obtained. Effects of various parameters like deposition overpotential, change of the substrate, deposition time, etc. on the particle size and shape were studied. It was found that a change of anions of the ionic liquid from acetate to nitrate results in a wide difference in the morphology of the deposits obtained. Acetate containing ionic liquids result in globular nanocrystalline deposits whereas nitrate containing ionic liquids result in flat plates or sheets of silver deposits. Similar results were obtained for silver sulphide nanocrystals. PMID:24394372

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  15. A classical density functional theory for interfacial layering of ionic liquids

    SciTech Connect

    Wu, Jianzhong; Jiang, Tao; Jiang, Deen; Jin, Zhehui; Henderson, Douglous

    2011-01-01

    Ionic liquids have attracted much recent theoretical interest for broad applications as environmentally-friendly solvents in separation and electrochemical processes. Because of the intrinsic complexity of organic ions and strong electrostatic correlations, the electrochemical properties of ionic liquids often defy the descriptions of conventional mean-field methods including the venerable, and over-used, Gouy-Chapman-Stern (GCS) theory. Classical density functional theory (DFT) has proven to be useful in previous studies of the electrostatic properties of aqueous electrolytes but until recently it has not been applied to ionic liquids. Here we report predictions from the DFT on the interfacial properties of ionic liquids near neutral or charged surfaces. By considering the molecular size, topology, and electrostatic correlations, we have examined major factors responsible for the unique features of electric-double layers of ionic-liquid including formation of long-range and alternating structures of cations and anions at charged surfaces.

  16. The configuration exchanging theory for transport properties and glass formation temperature of ionic liquids

    NASA Astrophysics Data System (ADS)

    Hu, Yu-Feng; Zhang, Xian-Ming; Qi, Jian-Guang; Yin, Liu-Yi

    2015-11-01

    Understanding molecular motion in terms of molecular structure is an important issue for microscopic understanding of the nature of transport properties and glass transition, and for design of structured materials to meet specific demands in various applications. Herein, a novel molecular mechanism is proposed to connect macroscopic motion in ionic liquids with molecular structure via conformational conversions of the constituent ions or of the cation-anion pairs. New equations for description of relaxation time, diffusion coefficient, molar conductivity, and viscosity of ionic liquids are established. The equation parameters, which were determined from the temperature dependent heat capacities, self-diffusion coefficients, molar conductivities, and viscosities of typical ionic liquids, were used to produce predictions for the corresponding properties of other ionic liquids and for the glass transition temperatures of representative ionic liquids. All predictions are in nice agreements with the experimental results.

  17. Atomic-scale characterization of oxide thin films gated by ionic liquid.

    PubMed

    Lang, Andrew C; Sloppy, Jennifer D; Ghassemi, Hessam; Devlin, Robert C; Sichel-Tissot, Rebecca J; Idrobo, Juan-Carlos; May, Steven J; Taheri, Mitra L

    2014-10-01

    Ionic liquids (ILs) have received considerable interest for use in electrostatic gating in complex oxide systems. Understanding the ionic liquid/oxide interface, and any bias-induced electrochemical degradation, is critical for the interpretation of transport phenomena. The integrity of the interface between ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate and La1/3Sr2/3FeO3 under various biasing conditions was examined by analytical transmission electron microscopy, and we report film degradation in the form of an irreversible chemical reaction regardless of the applied bias. This results in an intermixing region of 4-6 nm at the IL/oxide interface. Electron energy loss spectroscopy shows La and Fe migration into the ionic liquid, resulting in secondary phase formation under negative bias. Our approach can be extended to other ionic liquid/oxide systems in order to better understand the electrochemical stability window of these device structures. PMID:25188384

  18. Ion transport and softening in a polymerized ionic liquid.

    PubMed

    Kumar, Rajeev; Bocharova, Vera; Strelcov, Evgheni; Tselev, Alexander; Kravchenko, Ivan I; Berdzinski, Stefan; Strehmel, Veronika; Ovchinnikova, Olga S; Minutolo, Joseph A; Sangoro, Joshua R; Agapov, Alexander L; Sokolov, Alexei P; Kalinin, Sergei V; Sumpter, Bobby G

    2015-01-21

    Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this work, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current-voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as the Wien effect). Onsager's theory of the Wien effect coupled with the Poisson-Nernst-Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. The observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field. PMID:25463322

  19. Ion Transport in Polymerized Ionic Liquid Block and Random Copolymers

    NASA Astrophysics Data System (ADS)

    Elabd, Yossef; Ye, Yuesheng; Choi, Jae-Hong; Winey, Karen

    2012-02-01

    Polymerized ionic liquid (PIL) block copolymers, a new type of solid-state polymer electrolyte, are of interest for energy conversion and storage devices, such as fuel cells, batteries, supercapacitors, and solar cells. In this study, a series of PIL diblock and random copolymers with various PIL compositions were synthesized. These consisted of an IL monomer and a non-ionic monomer, 1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (MEBIm-TFSI) and methyl methacrylate (MMA), and 1-[(2-acryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (AEBIm-TFSI) and styrene (S), respectively, were synthesized. The anion conductivity (ion transport) and morphology were measured in all of the polymers with EIS, SAXS/WAXS, and TEM. Ion transport in block copolymers are significantly higher than random copolymers at the same PIL composition and are highly dependent on the block copolymer nanostructure. The relationship between ion transport mechanisms and the phase behavior of these materials will be discussed.

  20. Impedance spectroscopy investigation of liquid crystals doped with ionic surfactants

    NASA Astrophysics Data System (ADS)

    Belyaev, B. A.; Drokin, N. A.; Maslennikov, A. N.

    2014-07-01

    The effect of a direct-current (dc) electric field on the electrophysical characteristics of nematic liquid crystals of the alkyl cyanobiphenyl series nCB ( n = 6-8) and the multicomponent liquid-crystal mixture MB-1, which are doped with ionic surfactants, has been investigated using impedance spectroscopy. It has been found that the impedance spectra depend substantially on the dc bias voltage applied to the sample. The approximation of the measured spectra with specially developed equivalent circuits of the measuring cell with a sample has made it possible to determine the capacitance of the electric double layer and the electrical conductivity of the samples, as well as the mobility, concentration, and diffusion coefficient of the ions. It has been shown that a region of the space charge is formed in the frequency range f < 100 Hz near the electrodes of the measuring cell with a liquid-crystal sample, which leads to an increase in the active (resistive) and reactive (capacitive) components of the impedance.

  1. Concentrated assemblies of magnetic nanoparticles in ionic liquids.

    PubMed

    Mamusa, Marianna; Sirieix-Plnet, Juliette; Perzynski, Rgine; Cousin, Fabrice; Dubois, Emmanuelle; Peyre, Vronique

    2015-01-01

    Maghemite (?-Fe2O3) nanoparticles (NPs) can be successfully dispersed in a protic ionic liquid, ethylammonium nitrate (EAN), by transfer from aqueous dispersions into EAN. As the aqueous systems are well controlled, several parameters can be tuned. Their crucial role towards the interparticle potential and the structure of the dispersions is evidenced: (i) the size of the NPs tunes the interparticle attraction monitoring dispersions to be either monophasic or gas-liquid-like phase separated; (ii) the nature of the initial counterion in water (here sodium, lithium or ethylammonium) and the amount of added water (<20 vol%) modulate the interparticle repulsion. Very concentrated dispersions with a volume fraction of around 25% are obtained thanks to the gas-liquid-like phase separations. Such conclusions are derived from a fine structural and dynamical study of the dispersions on a large range of spatial scales by coupling several techniques: chemical analyses, optical microscopy, dynamic light scattering, magneto-optic birefringence and small angle scattering. PMID:25962152

  2. 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

  3. Saturation properties of 1-alkyl-3-methylimidazolium based ionic liquids.

    PubMed

    Rane, Kaustubh S; Errington, Jeffrey R

    2014-07-24

    We study the liquid-vapor saturation properties of room temperature ionic liquids (RTILs) belonging to the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) using Monte Carlo simulation. We examine the effect of temperature and cation alkyl chain length n on the saturated densities, vapor pressures, and enthalpies of vaporization. These properties are explicitly calculated for temperatures spanning from 280 to 1000 K for RTILs with n = 2, 4, 6, 8, 10, and 12. We also explore how the identity of the anion influences saturation properties. Specifically, we compare results for [C(4)mim][NTf2] with those for 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]). Simulations are completed with a recently developed realistic united-atom force field. A combination of direct grand canonical and isothermal-isobaric temperature expanded ensemble simulations are used to construct phase diagrams. Our results are compared with experimental data and Gibbs ensemble simulation data. Overall, we find good agreement between our results and those measured experimentally. We find that the vapor pressures and enthalpies of vaporization show a strong dependence on the size of the alkyl chain at low temperatures, whereas no particular trend is observed at high temperatures. Finally, we also discuss the effect of temperature on liquid phase nanodomains observed in RTILs with large hydrophobic groups. We do not observe a drastic change in liquid phase structure upon variation of the temperature, which suggests there is not a sharp phase transition between a nanostructured and homogeneous liquid, as has been suggested in earlier studies. PMID:24986360

  4. Multiple headspace extraction for gas detection in ionic liquids.

    PubMed

    Müller, D; Fühl, M; Pinkwart, K; Baltes, N

    2014-10-16

    In this study multiple headspace extraction was used for the first time to measure the saturation concentration of carbon monoxide and oxygen in various ionic liquids (ILs). Many processes in ILs involve the reaction of gases so that the reactant solubility is not a mere characteristical parameter, but understanding the solubility of gases in ILs is required for assessing the feasibility of possible applications. Multiple headspace extraction has proofed to be a powerful tool to obtain solubilities in good accordance with literature data. The measured saturation concentration for carbon monoxide and oxygen in ILs based on rarely researched tetracyanoborates and other anions was in the range of 1.5-6.5mmol/L. The great advantage of multiple headspace extraction is that it is a nonexpensive method that can be realised in most analytical laboratories by combination of a simple gas chromatograph and an eligible headspace injector. PMID:25458524

  5. Tunable wavelength soft photoionization of ionic liquid vapors

    SciTech Connect

    Strasser, Daniel; Goulay, Fabien; Belau, Leonid; Kostko, Oleg; Koh, Christine; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Ahmed, Musahid; Leone, Stephen R.

    2009-11-11

    Combined data of photoelectron spectra and photoionization efficiency curves in the near threshold ionization region of isolated ion-pairs from [emim][Tf2N], [emim][Pf2N]and [dmpim][Tf2N]ionic liquid vapors reveal small shifts in the ionization energies of ion-pair systems due to cation and anion substitutions. Shifts towards higher binding energy following anion substitution are attributed to increased electronegativity of the anion itself, while shifts towards lower binding energies following cation substitution are attributed to an increase in the cation-anion distance that causes a lower Coulombic binding potential. The predominant ionization mechanism in the near threshold photon energy region is identified as dissociative ionization, involving dissociation of the ion-pair and the production of intact cations as the positively charged products.

  6. Ionogels of a Sugar Surfactant in Ionic Liquids.

    PubMed

    Wang, Xiaolin; Yang, Qiao; Cao, Yixue; Zhou, Junhan; Hao, Haibin; Liang, Yuanyuan; Hao, Jingcheng

    2016-03-01

    Green and environmentally friendly ionogels formed by a sugar surfactant were prepared in two kinds of imidazolium-based ionic liquids. The phase transition from ribbon structures to lamellar structures induced by temperature and the transition mechanism were investigated in detail by means of freeze-fracture TEM and field-emission SEM observations, as well as small-angle X-ray scattering measurements. The rheological properties and tribological properties of two kinds of ionogels were systematically investigated. The difference in the lubricating properties and antiwear capability can be explained well by the mechanical and viscoelastic properties, as well as the different microstructures of samples destroyed by shear forces. This work provides a better understanding of the relationship between the structures, rheological properties, and tribological properties of ionogels. PMID:26647361

  7. Stable prenucleation mineral clusters are liquid-like ionic polymers

    PubMed Central

    Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.; Quigley, David; Gebauer, Denis

    2011-01-01

    Calcium carbonate is an abundant substance that can be created in several mineral forms by the reaction of dissolved carbon dioxide in water with calcium ions. Through biomineralization, organisms can harness and control this process to form various functional materials that can act as anything from shells through to lenses. The early stages of calcium carbonate formation have recently attracted attention as stable prenucleation clusters have been observed, contrary to classical models. Here we show, using computer simulations combined with the analysis of experimental data, that these mineral clusters are made of an ionic polymer, composed of alternating calcium and carbonate ions, with a dynamic topology consisting of chains, branches and rings. The existence of a disordered, flexible and strongly hydrated precursor provides a basis for explaining the formation of other liquid-like amorphous states of calcium carbonate, in addition to the non-classical behaviour during growth of amorphous calcium carbonate. PMID:22186886

  8. Homogeneous lithium electrodeposition with pyrrolidinium-based ionic liquid electrolytes.

    PubMed

    Grande, Lorenzo; von Zamory, Jan; Koch, Stephan L; Kalhoff, Julian; Paillard, Elie; Passerini, Stefano

    2015-03-18

    In this study, we report on the electroplating and stripping of lithium in two ionic liquid (IL) based electrolytes, namely N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl) imide (Pyr14FSI) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), and mixtures thereof, both on nickel and lithium electrodes. An improved method to evaluate the Li cycling efficiency confirmed that homogeneous electroplating (and stripping) of Li is possible with TFSI-based ILs. Moreover, the presence of native surface features on lithium, directly observable via scanning electron microscope imaging, was used to demonstrate the enhanced electrolyte interphase (SEI)-forming ability, that is, fast cathodic reactivity of this class of electrolytes and the suppressed dendrite growth. Finally, the induced inhomogeneous deposition enabled us to witness the SEI cracking and revealed previously unreported bundled Li fibers below the pre-existing SEI and nonrod-shaped protuberances resulting from Li extrusion. PMID:25714124

  9. Fabrication of ionic liquid ultrathin film by sequential deposition

    NASA Astrophysics Data System (ADS)

    Morino, Yusuke; Kanai, Yuta; Imanishi, Akihito; Yokota, Yasuyuki; Fukui, Ken-ichi

    2014-01-01

    A simple, mild, reproducible, and controllable nanodeposition method for ionic liquids (ILs) by ejection of IL solution through a high-speed electromagnetic valve (pulse valve) to a substrate under vacuum is proposed (pulse-valve method). Sequential deposition of an IL [1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIM-TFSI)] on Au(111) substrates from its methanol solution was examined by adopting the pulse-valve method and the deposited IL films were analyzed by X-ray photoelectron spectroscopy (XPS) and tapping-mode atomic force microscopy (AFM). The amount of IL deposited per a pulse was successfully reduced to less than an equivalent thickness of 0.2 nm. The deposited IL was homogeneously distributed over a substrate area of 1 1 cm2 substrate area and the deposited amount was reproducible for independent depositions.

  10. Ionic liquid-based green processes for energy production.

    PubMed

    Zhang, Suojiang; Sun, Jian; Zhang, Xiaochun; Xin, Jiayu; Miao, Qingqing; Wang, Jianji

    2014-11-21

    To mitigate the growing pressure on resource depletion and environment degradation, the development of green processes for the production of renewable energy is highly required. As a class of novel and promising media, ionic liquids (ILs) have shown infusive potential applications in energy production. Aiming to offer a critical overview regarding the new challenges and opportunities of ILs for developing green processes of renewable energy, this article emphasises the role of ILs as catalysts, solvents, or electrolytes in three broadly interesting energy production processes from renewable resources, such as CO2 conversion to fuels and fuel additives, biomass pretreatment and conversion to biofuels, as well as solar energy and energy storage. It is expected that this article will stimulate a generation of new ideas and new technologies in IL-based renewable energy production. PMID:24553494

  11. CO2 Chemistry of Phenolate-Based Ionic Liquids.

    PubMed

    Lee, Tae Bum; Oh, Seungmin; Gohndrone, Thomas R; Morales-Collazo, Oscar; Seo, Samuel; Brennecke, Joan F; Schneider, William F

    2016-03-01

    We synthesized ionic liquids (ILs) comprising an alkylphosphonium cation paired with phenolate, 4-nitrophenolate, and 4-methoxyphenolate anions that span a wide range of predicted reaction enthalpies with CO2. Each phenolate-based IL was characterized by spectroscopic techniques, and their physical properties (viscosity, conductivity, and CO2 solubility) were determined. We use the computational quantum chemical approach paired with experimental results to reveal the reaction mechanism of CO2 with phenolate ILs. Model chemistry shows that the oxygen atom of phenolate associates strongly with phosphonium cations and is able to deprotonate the cation to form an ylide with an affordable activation barrier. The ATR-FTIR and (31)P NMR spectra indicate that the phosphonium ylide formation and its reaction with CO2 are predominantly responsible for the observed CO2 uptake rather than direct anion-CO2 interaction. PMID:26556283

  12. Nanotribology of nanooxide materials in ionic liquids on silicon wafers

    NASA Astrophysics Data System (ADS)

    Hamidunsani, Ahmad Termizi; Radiman, Shahidan; Hassan, Masjuki Haji; Rahman, Irman Abdul

    2015-09-01

    Nanotribological properties have a significant impact on daily life. Ionic liquids (ILs) are becoming new favourable lubricants currently in researches. Addition of nanooxide materials in lubricants provide improvements to new technology. In this study, we determine nanotribological properties of BMIM+BF4- IL addition of different amount of ZnO nanomaterial on single crystals silicon wafer (Si110). The viscosity changes of IL samples against temperature increase were determined by rheological method. Nanotribological properties were determined by changes in friction coefficient and wear rate on silicon substrate surfaces using a reciprocating friction and wear monitor in 1 hour duration time. Aluminium cylinders acted as pins used to rub Si (110) substrate sample surfaces. Thus, on range between 0 mg to 3.5 mg of ZnO nanooxide material dispersed in 10ml BMIM+BF4- showed a good friction coefficient, wear and surface roughness reduction.

  13. Electrocapillary Curves for the Hg/Ionic Liquid Interface

    NASA Astrophysics Data System (ADS)

    Lewandowski, Andrzej; Majkowski, Tomasz; Galinski, Maciej

    2009-04-01

    Electrocapillary curves (surface tension ? as a function of the electrode potential E) for a series of room-temperature ionic liquids (RTILs) were measured using a mercury dropping electrode with the drop-weight (drop-volume) technique. The curves ? = f (E) for the Hg/RTIL interface have one maximum and may be approximated with a polynomial of sixth-order. There are no `humps' in the curves. The interfacial tension of the Hg/RTIL system changes with potential E in a monotonic way. The second derivative of ? = f (E) leads to a polynomial of fourth order, indicating the capacitance of the Hg/RTIL interface. The potential of zero charge is within a relatively narrow range. The specific capacitance at the minimum is of the order 10 ?F/cm2

  14. New models for predicting thermophysical properties of ionic liquid mixtures.

    PubMed

    Huang, Ying; Zhang, Xiangping; Zhao, Yongsheng; Zeng, Shaojuan; Dong, Haifeng; Zhang, Suojiang

    2015-10-28

    Potential applications of ILs require the knowledge of the physicochemical properties of ionic liquid (IL) mixtures. In this work, a series of semi-empirical models were developed to predict the density, surface tension, heat capacity and thermal conductivity of IL mixtures. Each semi-empirical model only contains one new characteristic parameter, which can be determined using one experimental data point. In addition, as another effective tool, artificial neural network (ANN) models were also established. The two kinds of models were verified by a total of 2304 experimental data points for binary mixtures of ILs and molecular compounds. The overall average absolute deviations (AARDs) of both the semi-empirical and ANN models are less than 2%. Compared to previously reported models, these new semi-empirical models require fewer adjustable parameters and can be applied in a wider range of applications. PMID:26399303

  15. Physicochemical properties of air and water stable rhenium ionic liquids.

    PubMed

    Fang, Da-Wei; Wang, Han; Yue, Shuang; Xiong, Ying; Yang, Jia-Zhen; Zang, Shu-Liang

    2012-03-01

    Air and water stable ionic liquids (ILs) based on catalytic functional metal rhenium, [C(n)mim][ReO(4)](n = 2,4,5,6)(1-alkyl-3-methylimidazolium perrhenate), are designed and synthesized. Their density and surface tension are measured in the temperature range of 293.15-343.15 0.05 K. Some physical-chemical properties of the ILs have been calculated or estimated by the empirical methods. The ion parachor is put forward and calculated by two extrathermodynamic assumptions. According to the interstice model, the thermal expansion coefficient of ILs [C(n)mim][ReO(4)], ?, are calculated and in comparison with experimental values, their magnitude order is in good agreement. PMID:22288875

  16. Development of regenerated cellulose/halloysites nanocomposites via ionic liquids.

    PubMed

    Hanid, Nurbaiti Abdul; Wahit, Mat Uzir; Guo, Qipeng; Mahmoodian, Shaya; Soheilmoghaddam, Mohammad

    2014-01-01

    In this study, regenerated cellulose/halloysites (RC/HNT) nanocomposites with different nanofillers loading were fabricated by dissolving the cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid. The films were prepared via solution casting method and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mechanical properties were investigated by tensile testing. It clearly displayed a good enhancement of both tensile strength and Young's modulus with HNT loading up to 5 wt%. As the HNT loadings increased to 5 wt%, the thermal behaviour and water resistance rate was also increased. The TEM and SEM images also depicted even dispersion of the HNT and a good intertubular interaction between the HNT and the cellulose matrix. PMID:24274483

  17. Viscosity mixing rules for binary systems containing one ionic liquid.

    PubMed

    Tariq, Mohammed; Altamash, Tausif; Salavera, Daniel; Coronas, Alberto; Rebelo, Luis P N; Canongia Lopes, Jose N

    2013-06-24

    In this work the applicability of four of the most commonly used viscosity mixing rules to [ionic liquid (IL)+molecular solvent (MS)] systems is assessed. More than one hundred (IL+MS) binary mixtures were selected from the literature to test the viscosity mixing rules proposed by 1) Hind (Hi), 2) Grunberg and Nissan (G-N), 3) Herric (He) and 4) Katti and Chaudhri (K-C). The analyses were performed by estimating the average (absolute or relative) deviations, AADs and ARDs, between the available experimental data and the predicted ideal mixture viscosity values obtained by means of each rule. The interaction terms corresponding to the adjustable parameters inherent to each rule were also calculated and their trends discussed. PMID:23650138

  18. Aggregation behavior of aqueous solutions of ionic liquids.

    PubMed

    Bowers, James; Butts, Craig P; Martin, Pamela J; Vergara-Gutierrez, Marcos C; Heenan, Richard K

    2004-03-16

    The aggregation behavior in aqueous solutions of three ionic liquids based on the 1-alkyl-3-methylimidazolium cation has been investigated by means of surface tension, conductivity, and small-angle neutron scattering (SANS) measurements. From analysis of the SANS data, models for the shapes and sizes of aggregates have been proposed: the short-chain 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim] [BF4] system can be best modeled by treating it as a dispersion of polydisperse spherical aggregates that form above a critical aggregation concentration, whereas the 1-octyl-3-methylimidazolium iodide, [C8mim] [I], solutions can be modeled as a system of regularly sized near-spherical charged micelles that form above a critical micelle concentration. Solutions of 1-octyl-3-methylimidazolium chloride, [C8mim]-[Cl], display weak long-range ordering of possibly disklike particles culminating in the formation of structures with distinct long-range order at higher concentrations. PMID:15835670

  19. Cyanoborohydride-based ionic liquids as green aerospace bipropellant fuels.

    PubMed

    Zhang, Qinghua; Yin, Ping; Zhang, Jiaheng; Shreeve, Jean'ne M

    2014-06-01

    In propellant systems, the most common bipropellants are composed of two chemicals, a fuel (or reducer) and an oxidizer. Currently, the choices for propellant fuels rely mainly on hydrazine and its methylated derivatives, even though they are extremely toxic, highly volatile, sensitive to adiabatic compression (risk of detonation), and, therefore, difficult to handle. With this background, the search for alternative green propellant fuels has been an urgent goal of space science. In this study, a new family of cyanoborohydride-based ionic liquids (ILs) with properties and performances comparable to hydrazine derivatives were designed and synthesized. These new ILs as bipropellant fuels, have some unique advantages including negligible vapor pressure, ultra-short ignition delay (ID) time, and reduced synthetic and storage costs, thereby showing great application potential as environmentally friendly fuels in bipropellant formulations. PMID:24737218

  20. Thermophysical properties of two ammonium-based protic ionic liquids

    PubMed Central

    Bhattacharjee, Arijit; Coutinho, João A. P.; Freire, Mara G.; Carvalho, Pedro J.

    2015-01-01

    Experimental data for density, viscosity, refractive index and surface tension are reported, for the first time, in the temperature range between 288.15 K and 353.15 K and at atmospheric pressure for two protic ionic liquids, namely 2-(dimethylamino)-N,N-dimethylethan-1-ammonium acetate, [N11{2(N11)}H][CH3CO2], and N-ethyl-N,N-dimethylammonium phenylacetate, [N112H][C7H7CO2]. The effect of the anion aromaticity and the cation’s aliphatic tails on the studied properties is discussed. From the measured properties temperature dependency the derived properties, such as the isobaric thermal expansion coefficient, the surface entropy and enthalpy, and the critical temperature, were estimated. PMID:26435554

  1. Printed environmentally friendly supercapacitors with ionic liquid electrolytes on paper

    NASA Astrophysics Data System (ADS)

    Pettersson, F.; Keskinen, J.; Remonen, T.; von Hertzen, L.; Jansson, E.; Tappura, K.; Zhang, Y.; Wiln, C.-E.; sterbacka, R.

    2014-12-01

    Environmentally friendly supercapacitors are fabricated using commercial grade aluminum coated paper as a substrate and symmetrical activated carbon electrodes as large area electrodes. Different choline chloride-based eutectic solvents are used as electrolyte. These are inexpensive, environmentally friendly and have a larger operating window compared to that of water electrolytes. As the entire device is printed and the materials used are inexpensive, both small- and large-area power sources can be fabricated to be used in cheap, disposable and recyclable devices. Supercapacitors with different eutectic solvents are measured using cyclic charge-discharge and impedance spectroscopy measurements and compared to one widely used and one green imidazolium ionic liquid; EMIM:TFSI and EcoEng 212, respectively. A mixture of ethylene glycol and choline chloride, Glyceline, show the highest capacitance and power densities of the electrolytes being tested, including the imidazolium alternatives.

  2. Enantioselective Nanoporous Carbon Based on Chiral Ionic Liquids.

    PubMed

    Fuchs, Ido; Fechler, Nina; Antonietti, Markus; Mastai, Yitzhak

    2016-01-01

    One of the greatest challenges in modern chemical processing is to achieve enantiospecific control in chemical reactions using chiral media such as chiral mesoporous materials. Herein, we describe a novel and effective synthetic pathway for the preparation of enantioselective nanoporous carbon, based on chiral ionic liquids (CILs). CILs of phenylalanine (CIL(Phe)) are used as precursors for the carbonization of chiral mesoporous carbon. We employ circular dichroism spectroscopy, isothermal titration calorimetry (ITC), and chronoamperometry in order to demonstrate the chiral nature of the mesoporous carbon. The approach presented in this paper is highly significant for the development of a new type of chiral porous materials for enantioselective chemistry. In addition, it contributes significantly to our understanding of the structure and nature of chiral nanoporous materials and surfaces. PMID:26556798

  3. Poly(ionic liquid) superabsorbent for polar organic solvents.

    PubMed

    Horne, W Jeffrey; Andrews, Mary A; Terrill, Kelsey L; Hayward, Spenser S; Marshall, Jeannie; Belmore, Kenneth A; Shannon, Matthew S; Bara, Jason E

    2015-05-01

    A simple, polymerized ionic liquid (poly(IL)) based on methylimidazolium cations tethered to a polystyrene backbone exhibits superabsorbent behavior toward polar organic solvents, most notably propylene carbonate (PC) and dimethyl sulfoxide (DMSO), wherein the poly(IL) was observed to swell more than 390 and 200 times (w/w) its original mass, yet absorbs negligible quantities of water, hexanes, and other solvents, many of which were miscible with the IL monomer. Although solubility parameters and dielectric constants are typically used to rationalize such behaviors, we find that poly(IL)-solvent compatibility is most clearly correlated to solvent dipole moment. Poly(IL) superabsorbency is not reliant upon the addition of a cross-linking agent. PMID:25893981

  4. Testing Fundamental Properties of Ionic Liquids for Colloid Microthruster Applications

    NASA Technical Reports Server (NTRS)

    Anderson, John R.; Plett, Gary; Anderson, Mark; Ziemer, John

    2006-01-01

    NASA's New Millennium Program is scheduled to test a Disturbance Reduction System (DRS) on Space Technology 7 (ST7) as part of the European Space Agency's (ESA's) LISA Pathfinder Mission in late 2009. Colloid Micronewton Thrusters (CMNTs) will be used to counteract forces, mainly solar photon pressure, that could disturb gravitational reference sensors as part of the DRS. The micronewton thrusters use an ionic liquid, a room temperature molten salt, as propellant. The ionic liquid has a number of unusual properties that have a direct impact on thruster design. One of the most important issues is bubble formation before and during operation, especially during rapid pressure transitions from atmospheric to vacuum conditions. Bubbles have been observed in the feed system causing variations in propellant flow rate that can adversely affect thruster control. Bubbles in the feed system can also increase the likelihood that propellant will spray onto surfaces that can eventually lead to shorting high voltage electrodes. Two approaches, reducing the probability of bubble formation and removing bubbles with a new bubble eliminator device in the flow system, were investigated at Busek Co., Inc. and the Jet Propulsion Laboratory (JPL) to determine the effectiveness of both approaches. Results show that bubble formation is mainly caused by operation at low pressure and volatile contaminants in the propellant coming out of solution. A specification for the maximum tolerable level of contamination has been developed, and procedures for providing system cleanliness have been tested and implemented. The bubble eliminator device has also been tested successfully and has been implemented in recent thruster designs at Busek. This paper focuses on the propellant testing work at JPL, including testing of a breadboard level bubble eliminator device.

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

    NASA Astrophysics Data System (ADS)

    Kornyshev, Alexei

    2010-03-01

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

  6. Evaluation of four ionic liquids for pretreatment of lignocellulosic biomass

    PubMed Central

    2014-01-01

    Background Lignocellulosic biomass is highly recalcitrant and various pretreatment techniques are needed to facilitate its effective enzymatic hydrolysis to produce sugars for further conversion to bio-based chemicals. Ionic liquids (ILs) are of interest in pretreatment because of their potential to dissolve lignocellulosic materials including crystalline cellulose. Results Four imidazolium-based ionic liquids (ILs) ([C=C2C1im][MeCO2], [C4C1im][MeCO2], [C4C1im][Cl], and [C4C1im][HSO4]) well known for their capability to dissolve lignocellulosic species were synthesized and then used for pretreatment of substrates prior to enzymatic hydrolysis. In order to achieve a broad evaluation, seven cellulosic, hemicellulosic and lignocellulosic substrates, crystalline as well as amorphous, were selected. The lignocellulosic substrates included hybrid aspen and Norway spruce. The monosaccharides in the enzymatic hydrolysate were determined using high-performance anion-exchange chromatography. The best results, as judged by the saccharification efficiency, were achieved with [C4C1im][Cl] for cellulosic substrates and with the acetate-based ILs for hybrid aspen and Norway spruce. After pretreatment with acetate-based ILs, the conversion to glucose of glucan in recalcitrant softwood lignocellulose reached similar levels as obtained with pure crystalline and amorphous cellulosic substrates. IL pretreatment of lignocellulose resulted in sugar yields comparable with that obtained with acidic pretreatment. Heterogeneous dissolution with [C4C1im][HSO4] gave promising results with aspen, the less recalcitrant of the two types of lignocellulose included in the investigation. Conclusions The ability of ILs to dissolve lignocellulosic biomass under gentle conditions and with little or no by-product formation contributes to making them highly interesting alternatives for pretreatment in processes where high product yields are of critical importance. PMID:24779378

  7. Selective Single-Step Separation of a Mixture of Three Metal Ions by a Triphasic Ionic-Liquid-Water-Ionic-Liquid Solvent Extraction System.

    PubMed

    Vander Hoogerstraete, Tom; Blockx, Jonas; De Coster, Hendrik; Binnemans, Koen

    2015-08-10

    In a conventional solvent extraction system, metal ions are distributed between two immiscible phases, typically an aqueous and an organic phase. In this paper, the proof-of-principle is given for the distribution of metal ions between three immiscible phases, two ionic liquid phases with an aqueous phase in between them. Three-liquid-phase solvent extraction allows separation of a mixture of three metal ions in a single step, whereas at least two steps are required to separate three metals in the case of two-liquid-phase solvent extraction. In the triphasic system, the lower organic phase is comprised of the ionic liquid betainium- or choline bis(trifluoromethylsulfonyl)imide, whereas the upper organic phase is comprised of the ionic liquid trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide. The triphasic system was used for the separation of a mixture of tin(II), yttrium(III), and scandium(III) ions. PMID:26178665

  8. Influence of Elemental Iodine on Imidazolium-Based Ionic Liquids: Solution and Solid-State Effects.

    PubMed

    Fei, Zhaofu; Bobbink, Flix D; P?unescu, Emilia; Scopelliti, Rosario; Dyson, Paul J

    2015-11-01

    Ionic liquids doped with I2, usually resulting in the formation of polyiodide anions, are extensively used as electrolytes and in iodination reactions. Herein, NMR spectroscopy and single-crystal X-ray diffraction were used to rationalize the structures of imidazolium-based polyiodide ionic liquids in the liquid and solid states. Combined, these studies show that extensive interactions between the imidazolium cation and the resulting polyiodide anion are present, which have the net effect of lengthening, polarizing, and weakening the I-I bonds in the anion. This bond weakening rationalizes the high conductivity and reactivity of ionic liquids doped with I2. PMID:26465973

  9. Ion transport and softening in a polymerized ionic liquid

    NASA Astrophysics Data System (ADS)

    Kumar, Rajeev; Bocharova, Vera; Strelcov, Evgheni; Tselev, Alexander; Kravchenko, Ivan I.; Berdzinski, Stefan; Strehmel, Veronika; Ovchinnikova, Olga S.; Minutolo, Joseph A.; Sangoro, Joshua R.; Agapov, Alexander L.; Sokolov, Alexei P.; Kalinin, Sergei V.; Sumpter, Bobby G.

    2014-12-01

    Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this work, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current-voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as the Wien effect). Onsager's theory of the Wien effect coupled with the Poisson-Nernst-Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. The observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field.Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this work, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current-voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as the Wien effect). Onsager's theory of the Wien effect coupled with the Poisson-Nernst-Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. The observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field. Electronic supplementary information (ESI) available: Details of the COMSOL modeling focusing on temperature distribution in polymer film under biased AFM tip, estimated of ionic conductivity using SPM and BDS measurements, Poisson-Nernst-Planck-Wien-Onsager model and thermodynamic description of the depression in melting due to the presence of ``free'' ions can be found in the ESI. See DOI: 10.1039/c4nr05491a

  10. Studies on the dissolution of glucose in ionic liquids and extraction using the antisolvent method.

    PubMed

    Hassan, El-Sayed R E; Mutelet, Fabrice; Pontvianne, Steve; Mose, Jean-Charles

    2013-03-19

    Biomass, the fibrous material derived from plant cell walls, is a potentially clean and renewable nonfood feedstock for liquid fuel and chemical production in future biorefineries. The capability of ionic liquids to act as selective solvents and catalysts for biomass processing has already been proven. Thus, they are considered as an alternative to conventional solvents. Nevertheless, phase equilibria with biomass derived compounds is still lacking in the literature. To overcome the lack of experimental data on phase equilibria of biomass carbohydrates in ionic liquids, the solubility of d-glucose in four ionic liquids was measured within a temperature range from 283 to 373 K. Solubility data were successfully correlated with local composition thermodynamic models such as NRTL and UNIQUAC. In this work, the possibility of extracting glucose from these ionic liquids using the antisolvent method has been also evaluated. The parameters affecting the extraction process are the ionic liquid type, ethanol/ionic liquid ratio, temperature, water content, and time. Results indicate that ethanol can be successfully used as an antisolvent to separate glucose from ionic liquids. PMID:23398175

  11. Prominent roles of impurities in ionic liquid for catalytic conversion of carbohydrates

    SciTech Connect

    Zhao, Haibo; Brown, Heather M.; Holladay, Johnathan E.; Zhang, Z. Conrad

    2012-02-07

    In the last two decades, ionic liquids have emerged as new and versatile solvents, and many of them are also catalysts for a broad range of catalytic reactions. Certain ionic liquids have been found to possess the unique capability of dissolving cellulosic biomass. The potential of such ionic liquids as solvent to enable catalytic conversion of cellulosic polymers was first explored and demonstrated by Zhao et al. This field of research has since experienced a rapid growth. Most ionic liquids have negligible vapor pressure and excellent thermal stability over a wide temperature range. For example, ionic liquids composed of 1-ethyl-3-methylimidazolium (EMIM+) cation and Cl- anion was reported to be stable up to 285 C, while salts of the same cation with other anions such as BF4- and PF6- are thermally stable above 380 C under inert atmosphere. It is well known that presence of impurities in ionic liquids typically causes changes in physical properties, e.g. decreasing in melting point and viscosity. Addition of Lewis acidic metal chlorides, e.g. AlCl3 to 1-alkyl-3-methylimidazolium chloride, [AMIM]Cl, is an exothermic reaction and considerably reduces the melting point by forming [AMIM]AlCl4 or [AMIM]Al2Cl7 that are also ionic liquids but have much lower melting point than the parent [AMIM]Cl. While most early research on catalysis of ionic liquids involving metallohalide anions were typically conducted from stoichiometric ratio of such anions to organic cations, e.g. [AMIM]+, the use of pure ionic liquids only as a solvent to carry out catalysis by a catalytic amount of a metal halide as catalyst truly displayed the solvent property of such ionic liquids.4 In such reaction systems, catalytic amounts of metal halides were used to catalyze the conversion of glucose and cellulose.4,11,12 The metal chloride catalyst concentration was in the order of 10-3 M. The presence of another metal chloride in the ionic liquids, even in the order of 10-5 M concentration was found to bring a dramatic synergistic effect. Therefore, the catalytic performance of the metal halide catalyst for the conversion of carbohydrates in the ionic liquid systems is highly sensitive to the presence of impurities. This work presents findings on the role of impurities that were present in some commercially available ionic liquids used for the conversion of the cellulose.

  12. Characterization of PVdF(HFP) gel electrolytes based on 1-(2-Hydroxyethyl)-3-methyl imidazolium ionic liquids.

    PubMed

    Yeon, Sun-Hwa; Kim, Ki-Sub; Choi, Sukjeong; Cha, Jong-Ho; Lee, Huen

    2005-09-29

    Poly(vinylidenefluoride)-hexafluoropropylene (PVdF(HFP))-ionic liquid gel electrolytes were prepared using ionic liquids based on 1-(2-hydroxyethyl)-3-methyl imidazolium tetrafluoroborate and 1-(2-hydroxyethyl)-3-methyl imidazolium hexafluorophosphate. A conventional metathesis reaction was used to prepare these ionic liquids, which have high purity and exhibit a liquid state at room temperature. The prepared polymer-ionic liquid gel proved to be a free-standing and rubbery film in which the degree of transparency differed according to the ratio and type of ionic liquid used. TGA and FTIR analyses confirmed that the solvent, N,N-Dimethylacetamide (DMAC), used for mixing PVdF(HFP) polymer with ionic liquid was almost totally removed during the gelling and drying processes. SEM photographs were taken of the surface structure of the PVdF(HFP)-ionic liquid gel in order to evaluate the morphology of the film's surface according to the mixing ratio and the nature of the ionic liquid. The thermal behaviors of PVdF(HFP)-ionic liquid gels were observed to be similar to those of neat ionic liquids through DSC analysis, and the compatibility between the polymer and ionic liquid was investigated by XRD analysis. The ionic conductivities of all the gels were 10(-3)-10(-5) S cm(-1) in a temperature range of 20-70 degrees C. PMID:16853301

  13. STRUCTURE AND PROPERTIES OF CORN, RICE, WHEAT AND POTATO STARCH DISPERSED IN THE IONIC LIQUID, 1-BUTYL-3-METHYLIMIDAZOLIUM CHLORIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ionic liquid has gained industry attention, especially in environmentally friendly green chemistry. Researchers have utilized ionic liquid for dispersing cellulose, but no report using ionic liquid for other polysaccharides. In this study, corn, rice, wheat and potato starches were dispersed in ho...

  14. A New Class of Solvents for TRU Dissolution and Separation: Ionic Liquids

    SciTech Connect

    Rogers, Robin D.

    2004-12-31

    Through the current EMSP funding, solvent extraction technologies based on liquid-liquid partitioning of TRU to an Ionic Liquid phase containing conventional complexants has been shown to be viable. The growing understanding of the role that the different components of an ionic liquid can have on the partitioning mechanism, and on the nature of the subsequent dissolved species indicates strongly that ionic liquids are not necessarily direct replacements for volatile or otherwise hazardous organic solvents. Separations and partitioning can be exceptionally complex with competing solvent extraction, cation, anion and sacrificial ion exchange mechanisms are all important, depending on the selection of components for formation of the ionic liquid phase, and that control of these competing mechanisms can be utilized to provide new, alternative separations schemes.

  15. 81891 - A New Class of Solvents for TRU Dissolution and Separation: Ionic Liquids

    SciTech Connect

    Robin D. Rogers

    2004-12-10

    Through the current EMSP funding, solvent extraction technologies based on liquid-liquid partitioning of TRU to an Ionic Liquid phase containing conventional complexants has been shown to be viable. The growing understanding of the role that the different components of an ionic liquid can have on the partitioning mechanism, and on the nature of the subsequent dissolved species indicates strongly that ionic liquids are not necessarily direct replacements for volatile or otherwise hazardous organic solvents. Separations and partitioning can be exceptionally complex with competing solvent extraction, cation, anion and sacrificial ion exchange mechanisms are all important, depending on the selection of components for formation of the ionic liquid phase, and that control of these competing mechanisms can be utilized to provide new, alternative separations schemes.

  16. Sonochemical formation of iron oxide nanoparticles in ionic liquids for magnetic liquid marble.

    PubMed

    Zhang, Shiguo; Zhang, Yan; Wang, Ying; Liu, Shimin; Deng, Youquan

    2012-04-21

    Ionic liquids (ILs)-stabilized iron oxide (Fe(2)O(3)) nanoparticles were synthesized by the ultrasonic decomposition of iron carbonyl precursors in [EMIm][BF(4)] without any stabilizing or capping agents. The Fe(2)O(3) nanoparticles were isolated and characterized by X-ray powder diffraction, transmission electron microscopy and susceptibility measurements. The physicochemical properties of ILs containing magnetic Fe(2)O(3) nanoparticles (denoted as Fe(2)O(3)@[EMIm][BF(4)]), including surface properties, density, viscosity and stability, were investigated in detail and compared with that of [EMIm][BF(4)]. The Fe(2)O(3)@[EMIm][BF(4)] can be directly used as magnetic ionic liquid marble by coating with hydrophobic and unreactive polytetrafluoroethylene (PTFE), for which the effective surface tension was determined by the puddle height method. The resulting magnetic ionic liquid marble can be transported under external magnetic actuation, without detachment of magnetic particles from the marble surface that is usually observed in water marble. PMID:22370757

  17. Pretreatment of lignocellulosic biomass with renewable cholinium ionic liquids: Biomass fractionation, enzymatic digestion and ionic liquid reuse.

    PubMed

    An, Yan-Xia; Zong, Min-Hua; Wu, Hong; Li, Ning

    2015-09-01

    Pretreatment of lignocelluloses is a key step in the biorefinery for production of biofuels and valuable platform chemicals. In this work, various lignocelluloses were pretreated using cholinium ionic liquids (ILs) that are wholly composed of biomaterials, and fractionated into carbohydrate-rich materials (CRMs) and lignin-rich materials (LRMs). Cholinium ILs were found to be effective pretreatment solvents for grass lignocelluloses as well as eucalyptus, resulting in significant improvements in the glucose yields (58-75%) in subsequent enzymatic hydrolysis, while they were inefficient to make pine susceptible to biodegradation. Approximately 46% of lignin in native rice straw was fractionated as LRM after pretreatment using cholinium argininate ([Ch][Arg]). [Ch][Arg] showed excellent recyclability, and the total recovery was as high as 75% after reused for 8 cycles. Besides, rice straw pretreated by the recycled IL remained highly digestible, and good glucose yields (63-75%) were achieved after its enzymatic hydrolysis. PMID:26026293

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  20. Determination of the enthalpy of vaporization and prediction of surface tension for ionic liquid 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6).

    PubMed

    Tong, Jing; Yang, Hong-Xu; Liu, Ru-Jing; Li, Chi; Xia, Li-Xin; Yang, Jia-Zhen

    2014-11-13

    With the use of isothermogravimetrical analysis, the enthalpies of vaporization, ?(g)lH(o)m(T(av)), at the average temperature, T(av) = 445.65 K, for the ionic liquids (ILs) 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6) were determined. Using Verevkin's method, the difference of heat capacities between the vapor phase and the liquid phase, ?(g)lC(p)(o)m, for [C(n)mim][Pro](n = 2, 3, 4, 5, 6), were calculated based on the statistical thermodynamics. Therefore, with the use of ?(g)lC(p)(o)m, the values of ?(g)lH(o)m(T(av)) were transformed into ?(g)lH(o)m(298), 126.8, 130.3, and 136.5 for [C(n)mim][Pro](n = 4, 5, 6), respectively. In terms of the new scale of polarity for ILs, the order of the polarity of [C(n)mim][Pro](n = 2, 3, 4, 5, 6) was predicted, that is, the polarity decreases with increasing methylene. A new model of the relationship between the surface tension and the enthalpy of vaporization for aprotic ILs was put forward and used to predict the surface tension for [C(n)mim][Pro](n = 2, 3, 4, 5, 6) and others. The predicted surface tension for the ILs is in good agreement with the experimental one. PMID:25350322