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Sample records for ionic liquid 1-ethyl-3-methylimidazolium

  1. Electrochemistry of tin in the 1-ethyl-3-methylimidazolium dicyanamide room temperature ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Leong, Tin-Iao; Hsieh, Yi-Ting [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan (China); Sun, I-Wen, E-mail: iwsun@mail.ncku.edu.t [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan (China)

    2011-04-15

    Research highlights: {yields} The electrochemistry of Sn(II) was studied in the room temperature ionic liquid 1-ethyl-3-methylimidazolium dicyanamide (EMI-DCA) on a glassy carbon (GC) and a polycrystalline Pt electrode at 40 {sup o}C. {yields} The Sn(II) species was introduced into the ionic liquid by either dissolution of SnCl{sub 2} or anodizing a Sn wire. {yields} The reduction potential of the Sn(II)/Sn couple produced in these two solutions was found to be different, indicating that different Sn(II) species may be present. {yields} The diffusion coefficient of SnCl{sub 2} dissolved in the EMI-DCA was in the same order of magnitude as those reported for SnCl{sub 2} in several other ionic liquids. {yields} Depending on the deposition potentials, potentiostatic electrolysis produced Sn deposits with various unusual morphologies such as hexagonal tubes, spiral nanowires, and dendrite. - Abstract: The electrochemistry of Sn(II) was studied in the room temperature ionic liquid 1-ethyl-3-methylimidazolium dicyanamide (EMI-DCA) on a glassy carbon (GC) and a polycrystalline Pt electrode at 40 {sup o}C. The Sn(II) species was introduced into the ionic liquid by either dissolution of SnCl{sub 2} or anodizing a Sn wire. The reduction potential of the Sn(II)/Sn couple produced in these two solutions was found to be different, indicating that different Sn(II) species may be present. The order of the reduction potential of the two Sn(II) species indicates that the Gutmann donor ability of the anions is likely to be DCA{sup -} > Cl{sup -}. Cyclic voltammetry indicates the stripping efficiency is >90% on the Pt but only 40% on the GC electrode. Analysis of the chronoamperometric transient behavior during electrodeposition suggests that the deposition of Sn on the GC electrode involves a three dimensional progressive nucleation on a finite number of active sites. The diffusion coefficient of SnCl{sub 2} dissolved in the EMI-DCA was found to be 9.8 x 10{sup -7} cm{sup 2} s

  2. Physical insight into switchgrass dissolution in the ionic liquid 1-ethyl-3-methylimidazolium acetate

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hui [University of Alabama, Tuscaloosa; Gurau, Gabriela [University of Alabama, Tuscaloosa; Pingali, Sai Venkatesh [ORNL; O' Neil, Hugh [ORNL; Evans, Barbara R [ORNL; Urban, Volker S [ORNL; Heller, William T [ORNL; Rogers, Robin D [University of Alabama, Tuscaloosa

    2014-01-01

    Small-angle neutron scattering was used to characterize solutions of switchgrass and the constituent biopolymers cellulose, hemicellulose, and lignin, as well as a physical mixture of them mimicking the composition of switchgrass, dissolved in the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate. The results demonstrate that the IL dissolves the cellulose fibrils of switchgrass, although a supramolecular biopolymer network remains that is not present in solutions of the individual biopolymers and that does not self-assemble in a solution containing the physical mixture of the individual biopolymers. The persistence of a network-like structure indicates that dissolving switchgrass in the IL does not disrupt all of the physical entanglements and covalent linkages between the biopolymers created during plant growth. Reconstitution of the IL-dissolved switchgrass yields carbohydrate-rich material containing cellulose with a low degree of crystallinity, as determined by powder X-ray diffraction, which impacts potential down-stream uses of the biopolymers produced by the process. The data suggests that the use of chemical additives which would break bonds that exist between the lignin and hemicellulose might improve the purity of the resulting product, but may not be able to disrupt the highly physically-entangled biopolymer network sufficiently to facilitate their separation.

  3. Impact of ionic liquid pretreatment conditions on cellulose crystalline structure using 1-ethyl-3-methylimidazolium acetate.

    Science.gov (United States)

    Cheng, Gang; Varanasi, Patanjali; Arora, Rohit; Stavila, Vitalie; Simmons, Blake A; Kent, Michael S; Singh, Seema

    2012-08-23

    Ionic liquids (ILs) have been shown to affect cellulose crystalline structure in lignocellulosic biomass during pretreatment. A systematic investigation of the swelling and dissolution processes associated with IL pretreatment is needed to better understand cellulose structural transformation. In this work, 3-20 wt % microcrystalline cellulose (Avicel) solutions were treated with 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) and a mixture of [C(2)mim][OAc] with the nonsolvent dimethyl sulfoxide (DMSO) at different temperatures. The dissolution process was slowed by decreasing the temperature and increasing cellulose loading, and was further retarded by addition of DMSO, enabling in-depth examination of the intermediate stages of dissolution. Results show that the cellulose I lattice expands and distorts prior to full dissolution in [C(2)mim][OAc] and that upon precipitation the former structure leads to a less ordered intermediate structure, whereas fully dissolved cellulose leads to a mixture of cellulose II and amorphous cellulose. Enzymatic hydrolysis was more rapid for the intermediate structure (crystallinity = 0.34) than for cellulose II (crystallinity = 0.54).

  4. Studies on electrical double layer capacitor with a low-viscosity ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate as electrolyte

    Indian Academy of Sciences (India)

    G P Pandey; S A Hashmi

    2013-08-01

    The performance of an electrical double layer capacitor (EDLC) composed of high surface area activated carbon electrodes and a new ionic liquid, 1-ethyl-3-methylimidazolium tetracyanoborate, [EMIm]TCB, as the electrolyte has been investigated by impedance spectroscopy, cyclic voltammetry and galvanostatic charge–discharge studies. The high ionic conductivity (∼1.3 × 10-2 S cm-1 at 20 °C) and low viscosity (∼22 cP) of the ionic liquid, [EMIm]TCB, make it attractive as electrolyte for its use in EDLCs. The optimum capacitance value of 195.5 F g-1 of activated carbon has been achieved with stable cyclic performance.

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

    Science.gov (United States)

    Das, Sudhir Kumar; Sarkar, Moloy

    2014-03-01

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

  6. Effect of the ionic liquid 1-ethyl-3-methylimidazolium acetate on the phase transition of starch: dissolution or gelatinization?

    Science.gov (United States)

    Mateyawa, Sainimili; Xie, David Fengwei; Truss, Rowan W; Halley, Peter J; Nicholson, Timothy M; Shamshina, Julia L; Rogers, Robin D; Boehm, Michael W; McNally, Tony

    2013-04-15

    This work revealed that the interactions between starch, the ionic liquid 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]), and water might contribute to the phase transition (gelatinization, dissolution, or both) of native starch at reduced temperature. Using mixtures of water and [Emim][OAc] at certain ratios (7.2/1 and 10.8/1 mol/mol), both the gelatinization and dissolution of the starch occur competitively, but also in a synergistic manner. At lower [Emim][OAc] concentration (water/[Emim][OAc] molar ratio≥25.0/1), mainly gelatinization occurs which is slightly impeded by the strong interaction between water and [Emim][OAc]; while at higher [Emim][OAc] concentration (water/[Emim][OAc] molar ratio≤2.8/1), the dissolution of starch is the major form of phase transition, possibly restricted by the difficulty of [Emim][OAc] to interact with starch. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Electroreduction of Benzoylformic Acid in 1-Ethyl-3-methylimidazolium Bromide Room Temperature Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    SUN Qian; ZHAO Peng; LU Jia-xing; HE Ming-yuan

    2005-01-01

    @@ Introduction The chemical industry is under considerable pressure to replace many volatile organic compounds that are widely used as solvents in organic synthesis. This trend leads to the exploration for novel reaction media. Room temperature ionic liquids as environmentally benign media for organic synthesis and catalytic reactions have been gradually recognized and accepted[1,2].

  8. Thermal Decomposition Mechanism of 1-ethyl-3-methylimidazolium Bromide Ionic Liquid (Preprint)

    Science.gov (United States)

    2011-09-14

    VUV -PI-TOFMS experiments were performed at the Chemical Dynamics beamline 9.0.2.3 at the Advanced Light Source synchrotron facility at the Lawrence... source VUV -PI-TOFMS experiments preclude the possibility of vaporization of EMIM+Br- as intact ion pairs. Instead, the observed photoions and PIE...Figure 3. VUV PI-TOFMS results for heated EMIM+Br- ionic liquid in an effusive source , with source temperature T=457 K. Photoion appearance energies

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Physical properties and solubility parameters of 1-ethyl-3-methylimidazolium based ionic liquids/DMSO mixtures at 298.15 K

    Science.gov (United States)

    Saba, H.; Yumei, Z.; Huaping, W.

    2015-12-01

    Densities, refractive indices, conductivities and viscosities of binary mixtures of 1-ethyl-3-methylimidazolium-based ionic liquids (ILs) with dimethyl sulfoxide at 298.15 K are reported. Excess molar volumes have been calculated from experimental data and were fitted with Redlich-Kister equation. The density and refractive index were found to increase with increasing concentration in all cases except [EMIM]COOH. The free mobility of ions has found to enhance conductivity and decrease viscosity to varying extent in all mixtures being studied. It has been observed that solubility parameters, dielectric constants and nature of anions of ILs being used play a vital role in determining the subsequent characteristics. As DMSO has high dielectric constant therefore, it was able to form interactions with most of ILs except with [EMIM]COOH due to anomalous nature of anion.

  11. Layering and shear properties of an ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate, confined to nano-films between mica surfaces.

    Science.gov (United States)

    Perkin, Susan; Albrecht, Tim; Klein, Jacob

    2010-02-14

    We report high-resolution measurements of the forces between two atomically smooth solid surfaces across a film of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid, for film thickness down to a single ion diameter. For films thinner than approximately 2 nm oscillatory structural forces are observed as the surface separation decreases and pairs of ion layers are squeezed out of the film. Strikingly, measurements of the shear stress of the ionic liquid film reveal low friction coefficients which are 1-2 orders of magnitude smaller than for analogous films of non-polar molecular liquids, including standard hydrocarbon lubricants, up to ca. 1 MPa pressure. We attribute this to the geometric and charge characteristics of the ionic liquid: the irregular shapes of the ions lead to a low shear stress, while the strong coulombic interactions between the ions and the charged confining surfaces lead to a robust film which is maintained between the shearing surfaces when pressure is applied across the film.

  12. Studies on the solvation dynamics of coumarin 153 in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: dependence on alkyl chain length.

    Science.gov (United States)

    Das, Sudhir Kumar; Sarkar, Moloy

    2012-08-06

    Steady-state and time-resolved fluorescence behavior of coumarin 153 (C153) is investigated in a series of 1-ethyl-3-methylimidazolium alkylsulfate ([C(2)mim][C(n)OSO(3)]) ionic liquids differing only in the length of the linear alkyl chain (n = 4, 6, and 8) in the anion. The aim of the present study is to understand the role of alkyl chain length in solute rotation and solvation dynamics of C153 in these ionic liquids. The blueshift observed in the steady-state absorption and emission maxima of C153 on going from the C(4)OSO(3) to the C(8)OSO(3) system indicates increasing nonpolar character of the microenvironment of the solute with increasing length of the alkyl side chain of the anion of the ionic liquids. The average solvation time is also found to increase on changing the substituent from butyl to octyl, and this is attributed to the increase in the bulk viscosity of the ILs. A steady blueshift of the time-zero maximum of the fluorescence spectrum with increasing alkyl chain length also indicates that the probe molecule experiences a less polar environment in the early part of the dynamics. Rotational dynamics of C153 are also analyzed by using the Stokes-Einstein-Debye (SED), Gierer-Wirtz (GW), and Dote-Kivelson-Schwartz (DKS) theories. Analyses of the results seem to suggest decoupling of the rotational motion of the probe from solvent viscosity.

  13. Synthesis of Highly Polymerized Water-soluble Cellulose Acetate by the Side Reaction in Carboxylate Ionic Liquid 1-ethyl-3-methylimidazolium Acetate

    Science.gov (United States)

    Pang, Jinhui; Liu, Xin; Yang, Jun; Lu, Fachuang; Wang, Bo; Xu, Feng; Ma, Mingguo; Zhang, Xueming

    2016-09-01

    In the present study, we describe a novel one-step method to prepare water-soluble cellulose acetate (WSCA) with higher degree of polymerization values (DP = 650–680) by in situ activation of carboxyl group in ionic liquid. First of all, cellulose was dissolved in 1-ethyl-3-methylimidazolium acetate (EmimAc) and reacted with dichloroacetyl chloride (Cl2AcCl) in order to make cellulose dichloroacetate. Under various conditions, a series of water soluble products were produced. Elemental analysis and NMR results confirmed that they were cellulose acetate with DS (degree of substitution) values in the range from 0.30 to 0.63. NMR studies demonstrated that Cl2AcCl reacted with acetate anion of EmimAc producing a mixed anhydride that acetylated cellulose. Other acylating reagents such as benzoyl chloride, chloroacetyl chloride can also work similarly. 2D NMR characterization suggested that 6-mono-O-acetyl moiety, 3,6-di-O-acetylcellulose and 2,6-di-O-acetyl cellulose were all synthesized and the reactivity of hydroxyl groups in anhydro-glucose units was in the order C-6>C-3>C-2. This work provides an alternative way to make WSCA, meanwhile, also services as a reminder that the activity of EmimAc toward carbohydrate as acylating reagents could be a problem, because the expected acylated products may not be resulted and recycling of this ionic liquid could also be difficult.

  14. Synthesis of Highly Polymerized Water-soluble Cellulose Acetate by the Side Reaction in Carboxylate Ionic Liquid 1-ethyl-3-methylimidazolium Acetate

    Science.gov (United States)

    Pang, Jinhui; Liu, Xin; Yang, Jun; Lu, Fachuang; Wang, Bo; Xu, Feng; Ma, Mingguo; Zhang, Xueming

    2016-01-01

    In the present study, we describe a novel one-step method to prepare water-soluble cellulose acetate (WSCA) with higher degree of polymerization values (DP = 650–680) by in situ activation of carboxyl group in ionic liquid. First of all, cellulose was dissolved in 1-ethyl-3-methylimidazolium acetate (EmimAc) and reacted with dichloroacetyl chloride (Cl2AcCl) in order to make cellulose dichloroacetate. Under various conditions, a series of water soluble products were produced. Elemental analysis and NMR results confirmed that they were cellulose acetate with DS (degree of substitution) values in the range from 0.30 to 0.63. NMR studies demonstrated that Cl2AcCl reacted with acetate anion of EmimAc producing a mixed anhydride that acetylated cellulose. Other acylating reagents such as benzoyl chloride, chloroacetyl chloride can also work similarly. 2D NMR characterization suggested that 6-mono-O-acetyl moiety, 3,6-di-O-acetylcellulose and 2,6-di-O-acetyl cellulose were all synthesized and the reactivity of hydroxyl groups in anhydro-glucose units was in the order C-6>C-3>C-2. This work provides an alternative way to make WSCA, meanwhile, also services as a reminder that the activity of EmimAc toward carbohydrate as acylating reagents could be a problem, because the expected acylated products may not be resulted and recycling of this ionic liquid could also be difficult. PMID:27644545

  15. Immobilization of laccase on modified silica: stabilization, thermal inactivation and kinetic behaviour in 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid.

    Science.gov (United States)

    Tavares, Ana P M; Rodríguez, Oscar; Fernández-Fernández, María; Domínguez, Alberto; Moldes, Diego; Sanromán, María A; Macedo, Eugénia A

    2013-03-01

    Laccase was immobilized on modified silica carrier. The immobilization conditions, pH and enzyme concentration were optimized. Operational stability of 10 reaction cycles showed that immobilized laccase in buffer was stable, presenting an activity loss 80% was obtained in ionic liquid (IL) solution. Activity of immobilized laccase was maintained when incubated in IL. After 7days of incubation, immobilized laccase lost 30-50% of its initial activity. Immobilization also improved thermal stability of laccase in the presence of IL. Enzyme kinetics was modelled with Michaelis-Menten model. The Km value for free laccase increases significantly with the IL concentration. Slight differences were found in Vm for free enzyme. Unusual kinetic behaviour was obtained for immobilized laccase in IL: Both Vm and Km increased with IL concentration, resulting in increased catalytic efficiency of the immobilized enzyme in presence of IL.

  16. Stability and kinetic behavior of immobilized laccase from Myceliophthora thermophila in the presence of the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate.

    Science.gov (United States)

    Fernández-Fernández, María; Moldes, Diego; Domínguez, Alberto; Sanromán, M Ángeles; Tavares, Ana Paula M; Rodríguez, Oscar; Macedo, Eugénia A

    2014-01-01

    The use of ionic liquids (ILs) as reaction media for enzymatic reactions has increased their potential because they can improve enzyme activity and stability. Kinetic and stability properties of immobilized commercial laccase from Myceliophthora thermophila in the water-soluble IL 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO4 ]) have been studied and compared with free laccase. Laccase immobilization was carried out by covalent binding on glyoxyl-agarose beads. The immobilization yield was 100%, and the activity was totally recovered. The Michaelis-Menten model fitted well to the kinetic data of enzymatic oxidation of a model substrate in the presence of the IL [emim][EtSO4 ]. When concentration of the IL was augmented, the values of Vmax for free and immobilized laccases showed an increase and slight decrease, respectively. The laccase-glyoxyl-agarose derivative improved the laccase stability in comparison with the free laccase regarding the enzymatic inactivation in [emim][EtSO4 ]. The stability of both free and immobilized laccase was slightly affected by small amounts of IL (<50%). A high concentration of the IL (75%) produced a large inactivation of free laccase. However, immobilization prevented deactivation beyond 50%. Free and immobilized laccase showed a first-order thermal inactivation profile between 55 and 70°C in the presence of the IL [emim][EtSO4 ]. Finally, thermal stability was scarcely affected by the presence of the IL.

  17. Microscopic structures of ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate in water probed by the relative chemical shift

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The relative chemical shifts (△δ) △δwere put forward to investigate the microscopic structure of 1-ethyl-3-methyl-imidazolium tetrafluoroborate (EmimBF4) during the dilution process with water.The concentration-dependent △δ(C2)H-(C4)H,△δ(C2)H-(C5)H and △δ(C4)H-(C5)H were analyzed.The results reveal that the variations of the microscopic structures of three aromatic protons are inconsistent.The strength of the H-bond between water and three aromatic protons follows the order:(C2)H···O > (C4)H···O > (C5)H···O.The concentration-dependent △δ(C6)H-(C7)H and △δ(C6)H-(C8)H indicate the formation of the H-bonds of (Calkyl)H···O is impossible,and more water is located around (C6)H than around (C7)H or (C8)H.The concentration-dependent △δ(C2)H-(C4)H and △δ(C2)H-(C5)H both increase rapidly when xwater > 0.9 or so,suggesting the ionic pairs of EmimBF4 are dissociated rapidly.The turning points of concentration-dependent △δ(C2)H-(C4)H and △δ(C2)H-(C5)H indicate that some physical properties of the EmimBF4/water mixtures also change at the corresponding concentration point.The microscopic structures of EmimBF4 in water could be clearly detected by the relative chemical shifts.

  18. Effect of adding ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate on the coordination environment of Li+ ions in propylene carbonate, according to data from IR spectroscopy and quantum chemical modeling

    Science.gov (United States)

    Shestakov, A. F.; Yudina, A. V.; Tulibaeva, G. Z.; Shul'ga, Yu. M.; Ignatova, A. A.; Yarmolenko, O. V.

    2017-08-01

    The effect ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate has on the coordination environment of Li+ cations in carbonate solvents is studied by means of IR spectroscopy and quantum chemical modeling using the example of propylene carbonate (PC). LiBF4 is used as the lithium salt. This system is promising for use as an electrolyte in lithium power sources (LPSs), but the mechanism of ionic conductivity by Li+ ions in such systems has yet to be studied in full.

  19. Phase Behaviour of 1-Ethyl-3-methylimidazolium Thiocyanate Ionic Liquid with Catalytic Deactivated Compounds and Water at Several Temperatures: Experiments and Theoretical Predictions

    Directory of Open Access Journals (Sweden)

    Ramalingam Anantharaj

    2011-01-01

    Full Text Available Density, surface tension and refractive index were determined for the binary mixture of catalytic deactivated compounds with 1-ethyl-3-methylimidazolium thiocyanate {[EMIM][SCN]} at temperature of (298.15 to 323.15 K. For all the compounds with ILs, the densities varied linearly in the entire mole fraction with increasing temperature. From the obtained data, the excess molar volume and deviation of surface tension and refractive index have been calculated. A strong interaction was found between similar (cation-thiophene or cation-pyrrole compounds. The interaction of IL with dissimilar compounds such as indoline and quinoline and other multiple ring compounds was found to strongly depend on the composition of IL at any temperatures. For the mixtures, the surface tension decreases in the order of: thiophene > quinoline > pyridine > indoline > pyrrole > water. In general from the excess volume studies, the IL-sulphur/nitrogen mixture has stronger interaction as compared to IL-IL, thiophene-thiophene or pyrrole-pyrrole interaction. The deviation of surface tension was found to be inversely proportional to deviation of refractive index. The quantum chemical based COSMO-RS was used to predict the non-ideal liquid phase activity coefficient for all mixtures. It indicated an inverse relation between activity coefficient and excess molar volumes.

  20. Local environment structure and dynamics of CO2 in the 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and related ionic liquids

    Science.gov (United States)

    Lourenço, Tuanan C.; Aparicio, Santiago; Costa, Gabriela C.; Costa, Luciano T.

    2017-03-01

    Despite the innumerous papers regarding the study of the ionic liquids as a potential candidate for CO2 capture, many details concerning the structure and dynamics of CO2 in the system are still to be revealed, i.e., the correlation between the local environment structure and the dynamic properties of the substance. This present work relied on the performance of molecular dynamics both for the neat [C2mim][Tf2N] and [C2mim][Tf2N]/CO2 mixtures in an attempt to elucidate the local environment of CO2 and their effects on the dynamic properties of [C2mim][Tf2N]. A slight change in the orientation of the cation and anion could be observed, which was correlated to the cation and anion moving away from each other in order to receive the carbon dioxide. The gas molecules pushed both the cation and the anion away to create sufficient void to its accommodation. The diffusion coefficient of [C2mim]+ is higher than [Tf2N]- regardless the increase of the CO2 concentration. The addition of CO2 in the ionic liquid has shown an increase of 4-5 times for the diffusivity of ions, which was related to the decrease of cation-anion interaction strength. The transport properties' results showed that the addition of CO2 in the ionic liquid generates the fluidization of the system, decreasing the viscosity as a consequence of the local environment structure changing. Likewise, the effect of the type of anion and cation on the system properties was studied considering [Ac]- and [BMpyr]+ ions, showing large effects by the change of anion to [Ac]- which rise from the strong [C2mim]+-[Ac]- interaction, which conditions the solvation of ions by CO2 molecules.

  1. Electrodeposition of Al in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids: in situ STM and EQCM studies.

    Science.gov (United States)

    Moustafa, E M; El Abedin, S Zein; Shkurankov, A; Zschippang, E; Saad, A Y; Bund, A; Endres, F

    2007-05-10

    In the present paper, the electrodeposition of Al on flame-annealed Au(111) and polycrystalline Au substrates in two air- and water-stable ionic liquids namely, 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]Tf(2)N, and 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]Tf(2)N, has been investigated by in situ scanning tunneling microscopy (STM), electrochemical quartz crystal microbalance (EQCM), and cyclic voltammetry. The cyclic voltammogram of aluminum deposition and stripping on Au(111) in the upper phase of the biphasic mixture of AlCl(3)/[EMIm]Tf(2)N at room temperature (25 degrees C) shows that the electrodeposition process is completely reversible as also evidenced by in situ STM and EQCM studies. Additionally, a cathodic peak at an electrode potential of about 0.55 V vs Al/Al(III) is correlated to the aluminum UPD process that was evidenced by in situ STM. A surface alloying of Al with Au at the early stage of deposition occurs. It has been found that the Au(111) surface is subject to a restructuring/reconstruction in the upper phase of the biphasic mixture of AlCl(3)/[Py(1,4)]Tf(2)N at room temperature (25 degrees C) and that the deposition is not fully reversible. Furthermore, the underpotential deposition of Al in [Py(1,4)]Tf(2)N is not as clear as in [EMIm]Tf(2)N. The frequency shift in the EQCM experiments in [Py(1,4)]Tf(2)N shows a surprising result as an increase in frequency and a decrease in damping with bulk aluminum deposition at potentials more negative than -1.8 V was observed at room temperature. However, at 100 degrees C there is a frequency decrease with ongoing Al deposition. At -2.0 V vs Al/Al(III), a bulk aluminum deposition sets in.

  2. Isobaric (vapor + liquid) equilibria of 1-ethyl-3-methylimidazolium ethylsulfate plus (propionaldehyde or valeraldehyde): Experimental data and prediction

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez, Victor H. [School of Chemical Engineering, University of Campinas (UNICAMP), Av. Albert Einstein 500, 13083-852 Campinas, SP (Brazil); Mattedi, Silvana [Chemical Engineering Department, Polytechnic School, Federal University of Bahia (UFBA), R. Aristides Novis 2, 40210-630 Salvador, BA (Brazil); Aznar, Martin, E-mail: maznar@feq.unicamp.b [School of Chemical Engineering, University of Campinas (UNICAMP), Av. Albert Einstein 500, 13083-852 Campinas, SP (Brazil)

    2011-06-15

    Research highlights: We report density, refraction index, and VLE for (propionaldehyde or valeraldehyde) + [emim][EtSO{sub 4}]. The Peng-Robinson + Wong-Sandler + COSMO-SAC model was used to predict density and VLE. The densities were predicted with deviations below than 2.3%. The experimental VLE was predicted with deviations below than 1.6%. - Abstract: This paper reports the density, refraction index, and (vapor + liquid) equilibria (VLE) for binary systems {l_brace}aldehyde + 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO{sub 4}]){r_brace}: {l_brace}propionaldehyde + [emim][EtSO{sub 4}]{r_brace} and {l_brace}valeraldehyde + [emim][EtSO{sub 4}]{r_brace}. The uncertainties for the temperature, pressure, and compositions measurements for the phase equilibria are {+-}0.1 K, {+-}0.01 kPa and {+-}0.0004, respectively. A qualitative analysis of the variation of the properties with changes in solvent and temperature was performed. The Peng-Robinson equation of state (PR EoS), coupled with the Wong-Sandler mixing rule (WS), is used to describe the experimental data. To calculate activity coefficients we used three different models: NRTL, UNIQUAC, and COSMO-SAC. Since the predictive liquid activity coefficient model COSMO-SAC is used in the Wong-Sandler mixing rule, the resulting thermodynamic model is a completely predictive one. The prediction results for the density and for the (vapor + liquid) equilibria have a deviation lower than 2.3% and 1.6%, respectively. The (vapor + liquid) equilibria predictions show a good description for the propionaldehyde system and only a qualitative description for the valeraldehyde system.

  3. Molecular Dynamics Studies on Liquid/Vapor Interface Properties and Structures of 1-Ethyl-3-methylimidazolium Dimethylphosphate-Water.

    Science.gov (United States)

    Li, Tianyu; Zhao, Zongchang; Zhang, Xiaodong; Sun, Xican

    2017-04-13

    1-Ethyl-3-methylimidazolium dimethylphosphate ([Emim][Dmp])-water binary solution is one of the promising new working-pairs for absorption heat pump and absorption chillers, which are widely used to recover industrial waste heat. In the absorption process, the mass and heat transfer at the interface greatly depend on interface microscopic structure. Therefore, in order to understand the absorption process, it is very important to study the interface microscopic structure. The liquid-vapor interface properties, as well as the orientation of [Emim](+), [Dmp](-), water at the interface and its aqueous solution with different water mole fraction, were studied using classical all-atom force field by molecular dynamic simulations. The simulated bulk mass density fitted by hyperbolic tangent function for each system was in good agreement with the experiment data, with the relative deviation between simulated and experimental value within 2%. The simulated results indicate that anion is always distributed at the outmost layer of the interface, followed by cation and water molecule. In [Emim][Dmp], the tilt angle of imidazolium rings to the surface normal is in the range of 0° interface, but almost all ethyl intend to tilt toward gas phase and the methyl tilt toward liquid bulk compared with pure [Emim][Dmp]. Two methyl in anion prefer to turn toward gas phase and its two PO vectors toward liquid bulk. This orientation indicates that pure [Emim][Dmp] absorb water in gas phase more easily than [Emim][Dmp]+H2O system does. Water molecules are distributed in the inner layer of the interface with two OH vectors (from O atom to H atom) tilting toward external surface.

  4. 离子液体1-乙基-3-甲基咪唑醋酸盐的制备及用于纤维素溶解纺丝的研究进展%Progress in Preparation of Ionic Liquid 1-Ethyl-3-Methylimidazolium Acetate and Application in Dissolution and Spinning of Cellulose

    Institute of Scientific and Technical Information of China (English)

    程春祖; 朱庆松; 孙玉山; 李晓俊; 徐纪刚

    2011-01-01

    离子液体1-乙基-3-甲基咪唑醋酸盐([EMIM3Ac)可以溶解天然高分子等许多聚合物,尤其对于纤维素具有较强的溶解能力,且溶解过程基本不造成纤维素降解,故可以作为纤维素的有效溶剂,用于纤维素的溶解加工。与其它溶剂相比,[EMIM]Ac具有使用安全、不污染环境、易回收循环利用等优势,故在纤维素溶解、纺丝方面具有广阔的应用前景。本文主要介绍了[EMIM]Ac的多种制备方法及其优缺点,这对其它醋酸盐类离子液体的制备也具有指导意义;并概述了[EMIM]Ac在纤维素溶解、纺丝等方面的应用研究。%Ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]Ae), which has stronger ability to dissolve cellulose especially, can be used to dissolve natural polymer and many other polymers. As the dissolving process of cellulose causes no degradation, [EMIM]Ac can be used as an effective solution in dissolving and proeessing of eellulose. Compared with other solutions, [EMIM]Ae has many advantages of use safety, no pollution to environment and easy recovery recycling, and has wide application prospect in the dissolving and spinning of cellulose. Various preparation methods of [EMIM]Ac and their advantages or disadvantages are introduced in this paper, which have a guiding significance to the preparations of other acetic acid salts ionic liquid. And the application research of [EMIM]Ac in cellulose dissolving and spinning is summarized.

  5. Structural analysis of 1-ethyl-3-methylimidazolium bifluoride melt

    Science.gov (United States)

    Matsumoto, Kazuhiko; Hagiwara, Rika; Ito, Yasuhiko; Kohara, Shinji; Suzuya, Kentaro

    2003-01-01

    The structure of 1-ethyl-3-methylimidazolium bifluoride (EMImF · HF) melt has been analyzed at 333 K by a high-energy synchrotron X-ray diffraction method. The total correlation function of the EMImF · HF melt was similar to that of the solid state, indicating that not only the short range but also the intermediate-range ordering in the solid are partially preserved in the liquid state. The intra-molecular F-F correlation in the anions clearly appears in the total correlation function of the EMImF · HF melt, whereas prominent peaks are not observed in the case of a room temperature molten salt, 1-ethyl-3-methylimidazolium fluorohydrogenate.

  6. Structural analysis of 1-ethyl-3-methylimidazolium bifluoride melt

    Energy Technology Data Exchange (ETDEWEB)

    Matsumoto, Kazuhiko; Hagiwara, Rika. E-mail: hagiwara@energy.kyoto-u.ac.jp; Ito, Yasuhiko; Kohara, Shinji; Suzuya, Kentaro

    2003-01-01

    The structure of 1-ethyl-3-methylimidazolium bifluoride (EMImF {center_dot} HF) melt has been analyzed at 333 K by a high-energy synchrotron X-ray diffraction method. The total correlation function of the EMImF {center_dot} HF melt was similar to that of the solid state, indicating that not only the short range but also the intermediate-range ordering in the solid are partially preserved in the liquid state. The intra-molecular F-F correlation in the anions clearly appears in the total correlation function of the EMImF {center_dot} HF melt, whereas prominent peaks are not observed in the case of a room temperature molten salt, 1-ethyl-3-methylimidazolium fluorohydrogenate.

  7. Measurement and Correlation of the Phase Diagram Data for 1-Ethyl-3-methylimidazolium Dimethyl phosphate+K3PO4/ K2HPOjK2CO3+ H20 Ionic Liquids Aqueous Two-Phase Systems at T-- 298.15 K%1-乙基-3-甲基咪唑磷酸二甲酯盐+K3P04/K2HP04/K2C03+H20离子液体双水相体系在T=298.15K时相图数据的测量和相关性

    Institute of Scientific and Technical Information of China (English)

    王良; 朱红; 闫永胜

    2012-01-01

    实验测定了1-乙基-3.甲基咪唑磷酸二甲酯盐(1-ethyl-3-methylimidazolium dimehtyl phosphate, [Emim]DMP )+盐(K3P04,K2HP04和K2C03)+H20体系在298.15K的双节点数据.用3个经验方程与双节点数据关联,发现Merchuk方程简便并且准确性好.不同盐的分相能力顺序为K3P04〉K2HP04〉K2C03,这与水合离子Gibbs自由能(△hydG)有关.用Othmer.Tobias方程、Bancroft方程和二元参数方程计算此方法和相应系线数据的可靠性.[Emim]DMP是常见的离子液体,广泛用于萃取石油燃料中的硫.报道T[Emim]DMP+盐+H20体系的相图数据.%Binodal data for the 1-ethyl-3-methylimidazolium dimethyl phosphate ([Emim]DMP)+salt (K3PO4, K2HPO4, and K2CO3)q-H20 systems were experimentally determined at 298.15 K. Three empirical equations were used to correlate binodal data. The Merchuk equation is an uncomplicated one for fine accu racy. The ability of different salts studied for phase separation are in the order of K3PO4 〉 K2HPO4 〉 K2CO3, which may be related to the Gibbs free energy of hydration of the ions (AhydG). The reliability of the calcula tion method and the corresponding tie-line data was described by the Othmer-Tobias equation and Bancroft equation, as well as the twoparameter equation. [Emim]DMP is a familiar ionic liquid, which is extensively used for extractive desulfurization of fuel oils. This is the first time to report the data for phase diagrams of [Emim]DMP 4- salt + water systems.

  8. Volatilization Mechanism of 1-Ethyl-3-methylimidazolium Bromide Ionic Liquid (Briefing Charts)

    Science.gov (United States)

    2012-04-01

    Distribution A: Approved for public release; distribution unlimited JPC -A 2008, 112, 7816 Hypergolic Ignition Autoignition at ambient P & T MMH...Tf2N]: 8.59 ± 0.03 eV PIE curves and structures C+A- + h C+A + e- C+ + A + e- JPC -A 2010, 114, 879 • Dissociative photoionization

  9. Enrichment, isolation and characterization of fungi tolerant to 1-ethyl-3-methylimidazolium acetate

    Energy Technology Data Exchange (ETDEWEB)

    Singer, S.W.; Reddy, A. P.; Gladden, J. M.; Guo, H.; Hazen, T.C.; Simmons, B. A.; VanderGheynst, J. S.

    2010-12-15

    This work aims to characterize microbial tolerance to 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), ionic liquid that has emerged as a novel biomass pretreatment for lignocellulosic biomass. Enrichment experiments performed using inocula treated with [C2mim][OAc] under solid and liquid cultivation yielded fungal populationsdominated by Aspergilli. Ionic liquid-tolerant Aspergillus isolates from these enrichments were capable of growing in a radial plate growth assay in the presence of 10% [C2mim][OAc]. When a [C2mim][OAc]-tolerant Aspergillus fumigatus strain was grown in the presence of switchgrass, endoglucanases and xylanases were secreted that retained residual enzymatic activity in the presence of 20% [C2mim][OAc]. The results of the study suggest tolerance to ionic liquids is a general property of Aspergilli. Tolerance to an industrially important ionic liquid was discovered in a fungal genera that is widely used in biotechnology, including biomass deconstruction.

  10. 1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

    Science.gov (United States)

    Ullah, Bakhtar; Chen, Jingwen; Zhang, Zhiguo; Xing, Huabin; Yang, Qiwei; Bao, Zongbi; Ren, Qilong

    2017-02-01

    1-Ethyl-3-methylimidazolium acetate is introduced as a robust organocatalyst for solvent-free cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN). The catalyst loading can be reduced to as low as 0.1-0.0001 mol % under mild reaction conditions, giving considerably high TOF values from 10,843 h-1 to 10,602,410 h-1 in the field of organocatalyzed transformations. The present protocol not only tolerates with extensive carbonyl compounds but also provides somewhat insight into the mechanism of ionic liquids (ILs)-catalyzed reactions.

  11. 1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

    Science.gov (United States)

    Ullah, Bakhtar; Chen, Jingwen; Zhang, Zhiguo; Xing, Huabin; Yang, Qiwei; Bao, Zongbi; Ren, Qilong

    2017-01-01

    1-Ethyl-3-methylimidazolium acetate is introduced as a robust organocatalyst for solvent-free cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN). The catalyst loading can be reduced to as low as 0.1–0.0001 mol % under mild reaction conditions, giving considerably high TOF values from 10,843 h−1 to 10,602,410 h−1 in the field of organocatalyzed transformations. The present protocol not only tolerates with extensive carbonyl compounds but also provides somewhat insight into the mechanism of ionic liquids (ILs)-catalyzed reactions. PMID:28198462

  12. Enzyme activity in dialkyl phosphate ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, M.F.; Dunn, J.; Li, L.-L.; Handley-Pendleton, J. M.; van der lelie, D.; Wishart, J. F.

    2011-12-01

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

  13. Enzyme activity in dialkyl phosphate ionic liquids.

    Science.gov (United States)

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

    2011-12-01

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

  14. Preparation of microfibers from wood/ionic liquid solutions.

    Science.gov (United States)

    Polaskova, Martina; Cermak, Roman; Verney, Vincent; Ponizil, Petr; Commereuc, Sophie; Gomes, Margarida F Costa; Padua, Agilio A H; Mokrejs, Pavel; Machovsky, Michal

    2013-01-30

    Two types of ionic liquids, 1-ethyl-3-methylimidazolim acetate and 1-ethyl-3-methylimidazolium lactate, were employed for the direct processing of pine wood into microfibers. The concentration of 5 wt.% of wood in ionic liquids was rated as the most appropriate for electrospinning. The fibers were electrospun into the collector water bath. The final structure varied from individual microfibers to fiber bundles. It was demonstrated that 1-ethyl-3-methylimidazolium lactate is a powerful solvent and provides the direct transformation of pristine pine wood into the non-wovens.

  15. "Practical" Electrospinning of Biopolymers in Ionic Liquids.

    Science.gov (United States)

    Shamshina, Julia L; Zavgorodnya, Oleksandra; Bonner, Jonathan R; Gurau, Gabriela; Di Nardo, Thomas; Rogers, Robin D

    2017-01-10

    To address the need to scale up technologies for electrospinning of biopolymers from ionic liquids to practical volumes, a setup for the multi-needle electrospinning of chitin using the ionic liquid 1-ethyl-3-methylimidazolium acetate, [C2 mim]-[OAc], was designed, built, and demonstrated. Materials with controllable and high surface area were prepared at the nanoscale using ionic-liquid solutions of high-molecular-weight chitin extracted with the same ionic liquid directly from shrimp shells.

  16. The effects of a co-solvent on fabrication of cellulose acetate membranes from solutions in 1-ethyl-3-methylimidazolium acetate

    KAUST Repository

    Kim, Dooli

    2016-08-15

    Ionic liquids have been considered green solvents for membrane fabrication. However, the high viscosity of their polymer solutions hinders the formation of membranes with strong mechanical properties. In this study, acetone was explored as a co-solvent with the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) to dissolve cellulose acetate. The effects of acetone on the thermodynamic and kinetic aspects of the polymer solutions were studied and the physicochemical properties and separation capability of their resultant membranes were analyzed. The Hansen solubility parameters of [EMIM]OAc were measured by the software HSPiP and these data demonstrated that acetone was a suitable co-solvent to increase the solubility of cellulose acetate. The Gibbs free energy of mixing ΔGm was estimated to determine the proper composition of the polymer solution with better solubility. The study of the kinetics of phase separation showed that the demixing rate of the CA polymer solution in acetone and [EMIM]OAc was higher than that for solutions in [EMIM]OAc only. The membranes prepared from the former solution had higher water permeance and better mechanical stability than those prepared from the later solution. Adding acetone as a co-solvent opened the opportunity of fabricating membranes with higher polymer concentrations for higher separation capability and better mechanical properties. © 2016

  17. Ternary liquid–liquid equilibria for mixtures of toluene + n-heptane + an ionic liquid

    NARCIS (Netherlands)

    Meindersma, G. Wytze; Podt, Anita J.G.; Haan, de André B.

    2006-01-01

    This research has been focused on a study of sulfolane and four ionic liquids as solvents in liquid–liquid extraction. Liquid–liquid equilibria data were obtained for mixtures of (sulfolane or 4-methyl-N-butylpyridinium tetrafluoroborate ([mebupy]BF4) or 1-ethyl-3-methylimidazolium ethylsulfate ([em

  18. Electropolymerization of O-Phenylenediamine in an Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    Yan Fang DU; Xi Min QI; Peng ZHAO; Jia Xing LU; Ming Yuan HE

    2004-01-01

    Ionic liquid like 1-ethyl-3-methylimidazolium bromine ([EMIM]Br) has been used as electrolyte for the electropolymerization of O-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It is found that poly (O-phenylenediamine) film modified electrode has favorable electrochemical activity in acid solution.

  19. Electrochemical performance of microporous and mesoporous activated carbons in neat and diluted 1-ethyl-3-methylimidazolium tetrafluoroborate

    Science.gov (United States)

    Kumagai, Seiji; Hatomi, Masaki; Tashima, Daisuke

    2017-03-01

    1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIm·BF4), neat and diluted with propylene carbonate to 1 mol L-1, have been employed as electrolytes of electrical double-layer capacitors (EDLCs). The effects of microporosity and mesoporosity in activated carbon (AC) electrodes on the capacitive and resistive performances upon the use of neat and diluted EMIm·BF4 have been explored. In addition to cyclic voltammetry and galvanostatic charge-discharge tests, electrochemical impedance spectroscopy has been performed employing Kang's equivalent circuit model consisting of three resistances, three constant phase elements, and one bounded Warburg impedance. The overall impedance of the EDLC cell was separated into components of intrinsic resistance, bulk electrolyte, diffusion layer, and Helmholtz layer. The specific capacitance and the equivalent series resistance (ESR) of mesoporous AC were found to be highly dependent on the rate of ionic transfer. Lower cell voltage was identified as being responsible for lower specific capacitance and larger ESR of mesoporous AC, which was similarly seen in the neat and diluted EMIm·BF4, and could be alleviated by increasing the cell voltage. The inferior rate performance and the cell-voltage-dependent performance of mesoporous AC, which were more distinctly observed in the neat EMIm·BF4, could be attributed to the lower mobility of EMIm+ and BF4- in mesopores.

  20. Electrochemistry in ultrahigh vacuum: underpotential deposition of Al on polycrystalline W and Au from room temperature AlCl(3)/1-ethyl-3-methylimidazolium chloride melts.

    Science.gov (United States)

    Johnston, Matthew; Lee, Jae-Joon; Chottiner, Gary S; Miller, Barry; Tsuda, Tetsuya; Hussey, Charles L; Scherson, Daniel A

    2005-06-09

    The voltammetric characteristics of polycrystalline Au and W electrodes cleaned (thermal annealing at 1100 K) and characterized (Auger electron spectroscopy) in ultrahigh vacuum (UHV) have been examined in ultrapure AlCl(3)/1-ethyl-3-methylimidazolium chloride (EtMeImCl) melts in UHV. These experiments were performed using a custom-designed transfer system that allows for the all-Al electrochemical cell to be filled with EtMeImCl in an auxiliary UHV chamber and later transferred under UHV to the main UHV chamber that houses the Auger electron spectrometer. The results obtained for the underpotential (UPD) and bulk deposition of Al on Au were found to be very similar to those reported in the literature for measurements carried out under 1 atm of an inert gas in a glovebox. For the far more reactive W surfaces, voltammetric features ascribed to the stripping of underpotential-deposited Al could be observed following a single scan from 1.0 V vs Al(3+)/Al to a potential negative enough for bulk deposition of Al to ensue. This behavior is unlike that reported in the literature for experiments performed in a glovebox, which required either extensive potential cycling in the Al bulk deposition and stripping region or excursions to potentials positive enough for chlorine evolution to ensue for Al UPD features to be clearly discerned. These observations open new prospects for fundamental electrochemical studies of well-characterized, highly reactive metals, including single crystals, in a variety of low vapor pressure ionic liquids.

  1. Thermodynamic properties of ternary mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate with 1-methyl pyrrolidin-2-one or pyrrolidin-2-one + water

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, V.K., E-mail: v_sharmachem58@rediffmail.com [Department of Chemistry, M. D. University, Rohtak, Haryana (India); Bhagour, S. [Department of Chemistry, M. D. University, Rohtak, Haryana (India); Sharma, D. [P.D.M. College of Engineering for Women, Bahadurgarh, Haryana (India); Solanki, S. [Department of Chemistry, M. D. University, Rohtak, Haryana (India)

    2013-07-10

    Highlights: • The V{sub ijk}{sup E} and (κ{sub S}{sup E}){sub ijk} data have been measured over entire mole fraction at 4 temperature. • The V{sub ijk}{sup E} and (κ{sub S}{sup E}){sub ijk} data have been fitted to Redlich–Kister equation. • The observed data have been analyzed in terms of Graph theory. • The V{sub ijk}{sup E} and (κ{sub S}{sup E}){sub ijk} values predicted by Graph theory compare well with experimental values. - Abstract: Densities, ρ{sub ijk} and speeds of sound, u{sub ijk} of 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + 1-methyl pyrrolidin-2-one or pyrrolidin-2-one (j) + water (k) ternary mixtures have been measured over the complete mole fraction range at 293.15, 298.15, 303.15, and 308.15 K using density and speed of sound analyzer (Anton Paar DSA 5000). The heat capacity, Cp of water at 293.15, 298.15, 303.15, and 308.15 K have also been measured using differential scanning calorimeter (Model – μDSC 7 Evo). The measured data have been employed to determine excess molar volumes, V{sub ijk}{sup E} and excess isentropic compressibilities, (κ{sub S}{sup E}){sub ijk}. The V{sub ijk}{sup E} and (κ{sub S}{sup E}){sub ijk} data have been fitted to Redlich–Kister equation to calculate ternary adjustable parameters and standard deviations. The observed thermodynamic properties of the ternary mixtures have been analyzed in terms of Graph theory. It has been observed that Graph theory successfully describes well V{sub ijk}{sup E} and (κ{sub S}{sup E}){sub ijk} data of the studied ternary ionic liquid mixtures.

  2. Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Jongerius, A.L.|info:eu-repo/dai/nl/325840202; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    Lignin is a component of lignocellulosic biomass from which important aromatic compounds can potentially be obtained. In the present work, Alcell and soda lignin were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP) and subsequently oxidized using several transit

  3. Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Jongerius, A.L.|info:eu-repo/dai/nl/325840202; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    Lignin is a component of lignocellulosic biomass from which important aromatic compounds can potentially be obtained. In the present work, Alcell and soda lignin were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP) and subsequently oxidized using several

  4. Dissolution and regeneration of microcrystalline cellulose in 1-ethyl-3-methylimidazolium diethylphosphate%微晶纤维素在EMIM-DEP中的溶解与再生

    Institute of Scientific and Technical Information of China (English)

    陶伟娜; 王少君; 李飞

    2012-01-01

    1-Ethyl-3-methylimidazolium diethylphosphate (EMIM-DEP) is synthesized with microwave method and is used to dissolve microcrystalline cellulose in this study. Its dissolution process is observed by polarizing microscope. With the rise of temperature the solubility of cellulose increases. Ultrasonic auxiliary can improve well the solubility of microcrystalline cellulose in ionic liquids. The regenerated cellulose is characterized by FT-IR, XRD, SEM and TGA. The results show that the microcrystalline cellulose in EMIM-DEP is dissolved directly without derivative reaction. The regenerated cellulose is changed from cellulose I into cellulose II in crystal style. Recovered ionic liquid has no change in structure and can be reused with good dissolving ability for microcrystalline cellulose.%通过微波法合成1-乙基-3-甲基咪唑磷酸二乙酯离子液体(EMIM-DEP)并用其溶解微晶纤维素.用偏光显微镜观察微晶纤维素在离子液体中的溶解.随温度的升高纤维素的溶解度增加,超声辅助可以很好地提高微晶纤维素在离子液体中的溶解度.溶解之后再生的纤维素通过红外光谱(FT-IR)、X-射线衍射(XRD)、扫描电镜(SEM)和热重分析(TGA)表征,结果显示微晶纤维素在EMIM-DEP中是直接溶解没有发生衍生反应;再生的纤维素晶型由纤维素Ⅰ型转化为纤维素Ⅱ型;回收后的离子液体结构没发生变化,重复利用仍保持较好的溶解微晶纤维素的能力.

  5. Investigation of Ternary Mixtures Containing 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonylazanide, Ethylene Carbonate and Lithium Bis(trifluoromethanesulfonylazanide

    Directory of Open Access Journals (Sweden)

    Andreas Hofmann

    2016-05-01

    Full Text Available Temperature-dependent viscosity, conductivity and density data of ternary mixtures containing 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonylazanide (EMIM-TFSA, ethylene carbonate (EC, and lithium bis(trifluoromethanesulfonylazanide (Li-TFSA were determined at atmospheric pressure in the temperature range of 20 to 80 °C. Differential scanning calorimetry (DSC measurements were performed to characterize phase conditions of the mixtures in a temperature range of −120 to +100 °C. The viscosity data were fitted according to the Vogel-Fulcher-Tammann-Hesse (VFTH equation and analyzed with the help of the fractional Walden rule. In this study, fundamental physicochemical data about the mixtures are provided and discussed as a basis for structure-property relationship calculations and for potential use of those mixtures as electrolytes for various applications.

  6. Structural characteristics of 1-ethyl-3-methylimidazolium bifluoride: HF-deficient form of a highly conductive room temperature molten salt

    Science.gov (United States)

    Matsumoto, Kazuhiko; Tsuda, Tetsuya; Hagiwara, Rika; Ito, Yasuhiko; Tamada, Osamu

    2002-01-01

    EMIF·HF, 1-ethyl-3-methylimidazolium bifluoride, has been obtained by eliminating HF from a room temperature molten salt EMIF·2.3HF at around 400 K. EMIF·HF crystallizes in space group P2 1/m with a=7.281(1) Å, b=6.762(1) Å, c=8.403(1) Å, β=107.26(1)°, V=395.09(18) Å 3, Z=2 at room temperature. The cations are stacked in pillars via the hydrogen bonding between the C4 proton and the ring π-electrons of the adjacent cation. The cations and the anions coupled by strong hydrogen bondings are co-planar.

  7. Physiochemical Properties of Hydrodenitrification and Hydrodesulphurization Inhibiting Compounds with 1-Ethyl-3-Methylimidazolium Ethylsulphate at T = (298.15 to 323.15 K and =1 Bar

    Directory of Open Access Journals (Sweden)

    Ramalingam Anantharaj

    2011-01-01

    Full Text Available This work investigates the ability of 1-ethyl-3-methylimidazolium ethylsulphate ([emim][EtSO4] as a green and tuneable solvent for denitrification and desulphurization of diesel oil. Experimental density, surface tension, and refractive index data have been measured for the following systems: [emim][EtSO4](1 + pyridine(2, [emim][EtSO4](1+ pyrrole(2, [emim][EtSO4](1 + quinoline(2, [emim][EtSO4](1 + indoline(2, [emim][EtSO4](1 + thiophene(2, and [emim][EtSO4](1 + water(2 over the entire mole fraction of [emim][EtSO4] at temperatures of (298.15 to 323.15 K and at atmospheric pressure. Further, from experimental density values, coefficient of thermal expansivity and excess molar volume were also calculated. It was found that the heteroaromatic nitrogen/sulphur compounds and water are completely miscible in the [emim][EtSO4] ionic liquid. The surface tension values were found to increase while the refractive index decrease with increasing mole fraction of [emim][EtSO4]. On the other hand, dissimilar molecule such as water showed mobility of ions on mixing resulting in lower surface tension. The experimental values of surface tension increased in the order: thiophene > pyridine > pyrrole > indoline > quinoline and for refractive index: quinoline > indoline > pyrrole > pyridine > thiophene > water. It was found that the composition of [emim][EtSO4] has a greater influence than temperature in deciding the densities, surface, optical, and thermodynamic properties.

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

    Science.gov (United States)

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

    2009-06-05

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

  9. Improvement of biomass properties by pretreatment with ionic liquids for bioconversion process.

    Science.gov (United States)

    Weerachanchai, Piyarat; Leong, Susanna Su Jan; Chang, Matthew Wook; Ching, Chi Bun; Lee, Jong-Min

    2012-05-01

    Cassava pulp residue and rice straw were used as a precursor for pretreatment with ionic liquids to study the effects of pretreatment conditions on product yield and properties. Cassava pulp residue is a potential biomass in the bioconversion process due to it requiring mild pretreatment conditions while providing a high sugar conversion. The maximum sugar conversion and lignin extraction are attained from pretreatment of biomasses with particle size of 1-Ethyl-3-methylimidazolium acetate at 120°C for 24h. The effectiveness of ionic liquid for biomass pretreatment process follows the sequence: 1-Ethyl-3-methylimidazolium acetate>1-Ethyl-3-methylimidazolium diethyl phosphate>1,3-Dimethylimidazolium methyl sulfate. The increase of pretreatment temperature from 25 to 120°C and decrease of biomass particle size renders higher sugar conversion, lignin extraction and lower crystallinity index. However, pretreatment at temperatures higher than 120°C shows a sharp decline of regenerated biomass yield, sugar conversion and lignin extraction and giving higher crystallinity index at pretreatment temperature of 180°C.

  10. The Preparation of Cellulose/Collagen Composite Films using 1-Ethyl-3-Methylimidazolium Acetate as a Solvent

    Directory of Open Access Journals (Sweden)

    Min Zhang

    2013-12-01

    Full Text Available Cellulose/collagen composite films with weight ratios of 30/1 (Blend-1 and 10/1 (Blend-2 were prepared using 1-ethyl-3-methylimidazolium acetate as a common solvent. The morphology of the films observed with a field-emission scanning electron microscope displayed a dependence on the ratio of cellulose/collagen. Collagen was successfully composited with cellulose without degradation and showed a denaturation temperature (Td higher than that of native collagen. Fourier transform infrared spectroscopy suggested that there were hydrogen-bond interactions between collagen and cellulose in the regenerated composite films. Thermogravimetric analysis revealed that the maximum decomposition temperature (Tmax of cellulose decreased after regeneration, while the Tmax of Blend-1 increased; however, it was reduced again for Blend-2. Elastic moduli from dynamic mechanical analysis exhibited a trend similar to that of Tmax. As indicated by X-ray diffraction, the distance between cellulose molecular chains was shortened for Blend-1 and elongated for Blend-2. Furthermore, the crystallization indices were calculated to be 75.3%, 68.3%, 66.2%, and 55.4% for native cellulose, regenerated films of cellulose, Blend-1, and Blend-2, respectively. These results confirm the dependence of the structural properties of composite films on cellulose/collagen ratios through the interactions between cellulose and collagen.

  11. Density and molar volumes of imidazolium-based ionic liquid mixtures and prediction by the Jouyban-Acree model

    Science.gov (United States)

    Ghani, Noraini Abd; Sairi, Nor Asrina; Mat, Ahmad Nazeer Che; Khoubnasabjafari, Mehry; Jouyban, Abolghasem

    2016-11-01

    The density of imidazolium-based ionic liquid, 1-ethyl-3-methylimidazolium diethylphosphate with sulfolane were measured at atmospheric pressure. The experiments were performed at T= (293 - 343) K over the complete mole fractions. Physical and thermodynamic properties such as molar volumes, V0, and excess molar volumes, VE for this binary mixtures were derived from the experimental density data. The Jouyban-Acree model was exploited to correlate the physicochemical properties (PCPs) of binary mixtures at various mole fractions and temperatures.

  12. Aqueous ionic liquid pretreatment of straw.

    Science.gov (United States)

    Fu, Dongbao; Mazza, Giuseppe

    2011-07-01

    Pretreatment is the key to unlock the recalcitrance of lignocellulose for cellulosic biofuels production. Increasing attention has been drawn to ionic liquids (ILs) for pretreatment of lignocellulosic biomass, because this approach has several advantages over conventional methods. However, cost and energy-intensive recycling of the solvents are major constraints preventing ILs from commercial viability. In this work, a mixture of ionic liquid 1-ethyl-3-methylimidazolium acetate and water was demonstrated to be effective for pretreatment of lignocellulosic biomass, evidenced by the removal of lignin and a reduction in cellulose crystallinity. A higher fermentable sugar yield (81%) was obtained than for pure ionic liquid pretreatment under the same conditions (67%). Aqueous ionic liquid pretreatment has the advantages of less usage and easier recycling of ILs, and reduced viscosity. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

  13. Enhanced enzymatic saccharification of kenaf powder after ultrasonic pretreatment in ionic liquids at room temperature.

    Science.gov (United States)

    Ninomiya, Kazuaki; Kamide, Kazuki; Takahashi, Kenji; Shimizu, Nobuaki

    2012-01-01

    This study demonstrates for the first time that the enzymatic hydrolysis of cellulose is drastically enhanced following ultrasonic pretreatment of lignocellulosic material in ionic liquids (ILs) when compared to conventional thermal pretreatment. Five types of ILs, 1-buthyl-3-methylimidazolium chloride (BmimCl), 1-allyl-3-methylimidazolium chloride (AmimCl), 1-ethyl-3-methylimidazolium chloride (EmimCl), 1-ethyl-3-methylimidazolium diethyl phosphate (EmimDep), and 1-ethyl-3-methylimidazolium acetate (EmimOAc) were tested. Cellulose saccharification ratio was about 20% for kenaf powders pretreated in BmimCl, AmimCl, EmimCl, and EmimDep by conventional heating at 110 °C for 120 min. Conversely, 60-95% of cellulose was hydrolyzed to glucose, subsequent to ultrasonic pretreatment in the same ILs for 120 min at 25 °C. The cellulose saccharification ratio of kenaf powder in EmimOAc was 86% after only 15 min of the ultrasonic pretreatment at 25 °C, compared to only 47% in that case of thermal pretreatment in the IL.

  14. A smart surface with switchable wettability by an ionic liquid.

    Science.gov (United States)

    Chang, Li; Liu, Hongliang; Ding, Yi; Zhang, Jiajing; Li, Li; Zhang, Xiqi; Liu, Mingzhu; Jiang, Lei

    2017-05-11

    Smart control of surface wettability by ionic liquids (ILs) is significant for designing IL-related intelligent materials and devices. Herein, we present mixed molecular brushes comprised of poly(phenylethyl methacrylate) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PPhEtMA-co-PFDMS) grafted surfaces that are capable of dynamically regulating 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2]) wettability. (1)H NMR and quartz crystal microbalance characterization demonstrate that the wettability changes result from a temperature-dominated cation-π interaction between [EMIm][NTf2] and PPhEtMA-co-PFDMS brushes.

  15. Optical absorption and fluorescence studies on imidazolium ionic liquids comprising the bis(trifluoromethanesulphonyl)imide anion

    Indian Academy of Sciences (India)

    Aniruddha Paul; Anunay Samanta

    2006-07-01

    Optical absorption and fluorescence behaviour of two rigorously purified imidazolium ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide are studied in the neat condition and in solution. Non-negligible absorption in the UV region with a long tail extending into the visible region is the main feature of the absorption. Excitation wavelength-dependent two-component fluorescence characterizes the emission behaviour of these liquids. That ion association gives rise to the long absorption tail and shifting fluorescence maximum, which appears to be common to most of the imidazolium ionic liquids, is evident from the effect of the conventional solvents.

  16. Investigation of polymer electrolyte based on agar and ionic liquids

    Directory of Open Access Journals (Sweden)

    M. M. Silva

    2012-12-01

    Full Text Available The possibility to use natural polymer as ionic conducting matrix was investigated in this study. Samples of agarbased electrolytes with different ionic liquids were prepared and characterized by physical and chemical analyses. The ionic liquids used in this work were 1-ethyl-3-methylimidazolium ethylsulfate, [C2mim][C2SO4], 1-ethyl-3-methylimidazolium acetate, [C2mim][OAc] and trimethyl-ethanolammonium acetate, [Ch][OAc]. Samples of solvent-free electrolytes were prepared and characterized by ionic conductivity measurements, thermal analysis, electrochemical stability, X-ray diffraction, scanning electron microscopy and Fourier Transform infrared spectroscopy. Electrolyte samples are thermally stable up to approximately 190°C. All the materials synthesized are semicrystalline. The electrochemical stability domain of all samples is about 2.0 V versus Li/Li+. The preliminary studies carried out with electrochromic devices (ECDs incorporating optimized compositions have confirmed that these materials may perform as satisfactory multifunctional component layers in the field of ‘smart windows’, as well as ECD-based devices.

  17. Corrosion behavior of construction materials for ionic liquid hydrogen compressor

    DEFF Research Database (Denmark)

    Arjomand Kermani, Nasrin; Petrushina, Irina; Nikiforov, Aleksey Valerievich

    2016-01-01

    The corrosion behavior of various commercially available stainless steels and nickel-based alloys as possible construction materials for components which are in direct contact with one of five different ionic liquids was evaluated. The ionic liquids, namely: 1-ethyl-3-methylimidazolium triflate, 1...... liquid hydrogen compressor. An electrochemical cell was specially designed, and steady-state cyclic voltammetry was used to measure the corrosion resistance of the alloys in the ionic liquids at 23 °C, under atmospheric pressure. The results showed a very high corrosion resistance and high stability...... for all the alloys tested. The two stainless steels, AISI 316L and AISI 347 showed higher corrosion resistance compared to AISI 321 in all the ionic liquids tested. It was observed that small addition of molybdenum, tantalum, and niobium to the alloys increased the corrosion stability in the ionic liquids...

  18. Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion-Pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

    Science.gov (United States)

    2013-09-01

    making ionic liquids potentially useful for batteries,3-5 solar cells,6, 7 fuel cells,8, 9 and as “green” solvents10 for organic synthesis and...ionic nature of the liquid. Earle and co-workers were the first to demonstrate, however, that the vacuum distillation of certain families of aprotic...Conversion Efficiency of Dye-Sensitized Solar Cells. J. Phys. Chem. B 2003, 107, 13280-13285.     7. Zakeeruddin, S. M.; Wang, P.; Wenger, B.; Humphry

  19. Probing Ionic Liquid Aqueous Solutions Using Temperature of Maximum Density Isotope Effects

    Directory of Open Access Journals (Sweden)

    Mohammad Tariq

    2013-03-01

    Full Text Available This work is a new development of an extensive research program that is investigating for the first time shifts in the temperature of maximum density (TMD of aqueous solutions caused by ionic liquid solutes. In the present case we have compared the shifts caused by three ionic liquid solutes with a common cation—1-ethyl-3-methylimidazolium coupled with acetate, ethylsulfate and tetracyanoborate anions—in normal and deuterated water solutions. The observed differences are discussed in terms of the nature of the corresponding anion-water interactions.

  20. Recyclability of an ionic liquid for biomass pretreatment.

    Science.gov (United States)

    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).

  1. Dissolution enthalpies of cellulose in ionic liquids.

    Science.gov (United States)

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

    2014-11-26

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

  2. Oxidative depolymerization of lignin in ionic liquids.

    Science.gov (United States)

    Stärk, Kerstin; Taccardi, Nicola; Bösmann, Andreas; Wasserscheid, Peter

    2010-06-21

    Beech lignin was oxidatively cleaved in ionic liquids to give phenols, unsaturated propylaromatics, and aromatic aldehydes. A multiparallel batch reactor system was used to screen different ionic liquids and metal catalysts. Mn(NO(3))(2) in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [EMIM][CF(3)SO(3)] proved to be the most effective reaction system. A larger scale batch reaction with this system in a 300 mL autoclave (11 g lignin starting material) resulted in a maximum conversion of 66.3 % (24 h at 100 degrees C, 84x10(5) Pa air). By adjusting the reaction conditions and catalyst loading, the selectivity of the process could be shifted from syringaldehyde as the predominant product to 2,6-dimethoxy-1,4-benzoquinone (DMBQ). Surprisingly, the latter could be isolated as a pure substance in 11.5 wt % overall yield by a simple extraction/crystallization process.

  3. Phase equilibria in ionic liquid-aromatic compound mixtures, including benzene fluorination effects.

    Science.gov (United States)

    Blesic, Marijana; Lopes, José N Canongia; Pádua, Agílio A H; Shimizu, Karina; Gomes, Margarida F Costa; Rebelo, Luís Paulo N

    2009-05-28

    This work extends the scope of previous studies on the phase behavior of mixtures of ionic liquids with benzenes or its derivatives by determining the solid-liquid and liquid-liquid phase diagrams of mixtures containing an ionic liquid and a fluorinated benzene. The systems studied include 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide plus hexafluorobenzene or 1,3,5-trifluorobenzene and 1-ethyl-3-methylimidazolium triflate or N-ethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide plus benzene. The phase diagrams exhibit different kinds of solid-liquid behavior: the (usual) occurrence of eutectic points; the (not-so-usual) presence of congruent melting points and the corresponding formation of inclusion crystals; or the observation of different ionic liquid crystalline phases (polymorphism). These different types of behavior can be controlled by temperature annealing during crystallization or by the nature of the aromatic compound and can be interpreted, at a molecular level, taking into account the structure of the crystals or liquid mixtures, together with the unique characteristics of ionic liquids, namely the dual nature of their interactions with aromatic compounds.

  4. Separation of Guanine and Hypoxanthine with Some Ionic Liquids in RP-HPLC

    Directory of Open Access Journals (Sweden)

    J. Zheng

    2006-01-01

    Full Text Available In this paper, guanine and hypoxanthine were separated with four different ionic liquids as additives for the mobile phase using reversed phase high performance liquid chromatography (RP-HPLC. The ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4], 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIm][BF4], 1-ethyl-3-methylimidazolium methylsulfate ([EMIm][MS] and 1-octyl-3-methylimidazolium methylsulfate ([OMIm][MS] were used. Guanine and hypoxanthine couldn’t be separated with many different kinds of unadjusted mobile phase, such as aqueous-methanol, aqueous-acetonitrile, etc. In this reason, present study introduced the ionic liquid for separation of guanine and hypoxanthine as an eluent modifier. And the effects of length of alkyl on the imidazolium ring and its counterion, the concentrations of ionic liquid on the retention factor and effect of pH of mobile phase on retention factor of solutes were investigated also. As a result, guanine and hypoxanthine were separated with the mobile phase including ionic liquid and the excellent separations of these sorbats were achieved using 2.0 mM Lˉ1 [OMIm][MS] as the eluent modifier.

  5. Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    CAI,Qing-Hai(蔡清海); ZHANG,Li(张丽); SHAN,Yong-Kui(单永奎); HE,Ming-Yuan(何鸣元)

    2004-01-01

    Promotion of ionic liquid,1-ethyl-3-methylimidazolium bromide (emimBr),to the synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the presence of potassium carbonate and less amount of methyl iodide under mild conditions was investigated.The results showed that the high selectivity and raised yield of DMC was achieved due to the addition of emimBr in the reaction system.And effect of several reaction conditions such as temperature,pressure and amount of emimBr was discussed.

  6. Molecular ions of ionic liquids in the gas phase.

    Science.gov (United States)

    Gross, Jürgen H

    2008-09-01

    Ionic liquids form neutral ion pairs (CA) upon evaporation. The softness of the gas-phase ionization of field ionization has been used to generate "molecular ions," CA(+*), of ionic liquids, most probably by neutralization of the anion. In detail, 1-ethyl-3-methylimidazolium-thiocyanate, [C(6)H(11)N(2)](+) [SCN](-), 1-butyl-3-methylimidazolium-tricyanomethide, [C(8)H(15)N(2)](+) [C(4)N(3)](-), N-butyl-3-methylpyridinium-dicyanamide, [C(10)H(16)N](+) [C(2)N(3)](-), and 1-butyl-1-methylpyrrolidinium-bis[(trifluormethyl)sulfonyl]amide, [C(9)H(20)N](+) [C(2)F(6)NO(4)S(2)](-) were used. The assignment as CA(+*) ions, which has been confirmed by accurate mass measurements and misassignments due to thermal decomposition of the ionic liquids, has been ruled out by field desorption and electrospray ionization mass spectrometry of the residues.

  7. Comparison Study of Different Ionic Liquid Pretreatments in Maximizing Total Reducing Sugars Recovery

    Directory of Open Access Journals (Sweden)

    Kiat Moon Lee

    2014-01-01

    Full Text Available A process scheme combining the most suitable ionic liquid pretreatment, followed by solid acid and enzymatic saccharification was used to maximize the reducing sugars recovery from sago waste. Three types of ionic liquids, i.e. 1-butyl-3-methylimidazolium chloride ([BMIM]Cl, 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc] and 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM][(EtO2PO2] were evaluated based on their performance in terms of the total reducing sugars recovery, chemical cost, and pretreatment energy requirement. The results showed that all the ionic liquids assisted the saccharification processes by dissolving and depolymerizing the carbohydrates of the sago waste into shorter chain soluble oligosaccharides, as well as disrupting the biomass structure to produce an amorphous pretreated solid residue. The solid acid saccharifications of the prehydrolysates obtained from the [BMIM]Cl pretreatment gave the highest reducing sugars recovery (61-63% irrespective of the solid acid catalyst employed. On the other hand, enzymatic saccharification of [EMIM][OAc] pretreated solid residues showed the highest reducing sugars recovery (29%. A maximum recovery of 90% reducing sugars was achieved via incorporation of the ionic liquid pretreatment, solid acid and enzymatic saccharifications using [BMIM]Cl, Amberlyst 15 (A15 and Trichoderma viride cellulase respectively. This study suggests that the combined sequential process can maximize the reducing sugars recovery from sago waste effectively.

  8. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    Science.gov (United States)

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W

    2015-11-19

    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  9. Ionic Liquid based polymer electrolytes for electrochemical sensors

    Directory of Open Access Journals (Sweden)

    Jakub Altšmíd

    2015-09-01

    Full Text Available Amperometric NO2 printed sensor with a new type of solid polymer electrolyte and a carbon working electrode has been developed. The electrolytes based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide [EMIM][N(Tf2], 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][CF3SO3] and 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF4] ionic liquids were immobilized in poly(vinylidene fluoride matrix [PVDF]. The analyte, gaseous nitrogen dioxide, was detected by reduction at -500 mV vs. platinum pseudoreference electrode. The sensors showed a linear behavior in the whole tested range, i.e., 0 - 5 ppm and their sensitivities were in order of 0.3 x∙10-6 A/ppm. The sensor sensitivity was influenced by the electric conductivity of printing formulation; the higher the conductivity, the higher the sensor sensitivity. The rise/recovery times were in order of tens of seconds. The use of  screen printing technology and platinum pseudoreference electrode simplify the sensor fabrication and it does not have any negative effect on the sensor stability.DOI: http://dx.doi.org/10.5755/j01.ms.21.3.7371

  10. Nanocrystalline porous TiO2 electrode with ionic liquid impregnated solid polymer electrolyte for dye sensitized solar cells.

    Science.gov (United States)

    Singh, Pramod K; Kim, Kang-Wook; Kim, Ki-Il; Park, Nam-Gyu; Rhee, Hee-Woo

    2008-10-01

    This communication reports the detailed fabrication of electrodes and solid polymer electrolyte with ionic liquid (IL) as an electrolyte for dye sensitized solar cell (DSSC). Thick porous TiO2 film has been obtained by spreading and sintering TiO2 colloidal paste using "doctor blade" and characterized by SEM, TEM and XRD. The polymer electrolyte was PEO:KI/I2 incorporated with 1-ethyl 3-methylimidazolium thiocyanate (EMImSCN) as IL. Dispersal of IL in the polymer electrolyte improved the ionic conductivity and cell efficiency.

  11. Synergistic Effect of Combining Titanosilicate and 1-Ethyl-3-Methylimidazolium Acetate in Mixed Matrix Membranes for Efficient C02 Separation

    Directory of Open Access Journals (Sweden)

    Maria Del Mar López Guerrero

    2015-06-01

    Full Text Available The separation and capture of CO2 from these sources is becoming important for greenhouse emission. The membrane-based separation process use to remove CO2 takes advantages in energy efficient and environmentally friendly aspects and has been recognized as an important technology for CO2 capture and gas separation. The novel mixed matrix membranes (MMMs were fabricated by incorporating microporous titanosilicate ETS-10 and a highly CO2 absorbent ionic liquid , [EMIM][Ac] into a Chitosan (CS matrix to improve CO2 separation performance, and were prepared, characterized and tested for CO2 and N2. The solubility values show that the CO2 solubility increases upon addition of ETS-10 particles. The N2 solubility in the ETS-10/[EMIM][Ac]/CS was reduced, while CO2 solubility remained constant. FT-IR spectra revealed a good interaction between the components in the MMMs. Subtle differences in the intensity and position of all individual bands, were observed in the region between 3600 and 2700 cm-1 and 1700 and 900 cm-1. These indicated bonding of the components in the film, confirming the good interaction existing among the components, and that may account for the higher flexibility of the hybrid membrane materials imparted to both CS and ETS-10/CS MMMs, , due to the singular interaction between CS and [EMIM][Ac]. Keywords: CO2 solubility, CO2 separation, microporous titanosilicate ETS-10, Chitosan, mixed matrix membranes (MMMs.

  12. Influences of porous reservoir Laplace pressure on emissions from passively fed ionic liquid electrospray sources

    Energy Technology Data Exchange (ETDEWEB)

    Courtney, Daniel G., E-mail: dcourtney@alum.mit.edu; Shea, Herbert [Ecole Polytechnique Federale de Lausanne (EPFL), Microsystems for Space Technologies Laboratory (LMTS), Neuchatel CH-2002 (Switzerland)

    2015-09-07

    Passively fed ionic liquid electrospray sources are capable of efficiently emitting a variety of ion beams with promising applications to spacecraft propulsion and as focused ion beams. Practical devices will require integrated or coupled ionic liquid reservoirs; the effects of which have not been explored in detail. Porous reservoirs are a simple, scalable solution. However, we have shown that their pore size can dramatically alter the beam composition. Emitting the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide, the same device was shown to yield either an ion or droplet dominated beam when using reservoirs of small or large pore size, respectively; with the latter having a mass flow in excess of 15 times larger than the former at negative polarity. Another source, emitting nearly purely ionic beams of 1-ethyl-3-methylimidazolium tetrafluoroborate, was similarly shown to emit a significant droplet population when coupled to reservoirs of large (>100 μm) pores; constituting a reduction in propulsive efficiency from greater than 70% to less than 30%. Furthermore, we show that reservoir selection can alter the voltage required to obtain and sustain emission, increasing with smaller pore size.

  13. Pretreatment of rice hulls by ionic liquid dissolution.

    Science.gov (United States)

    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.

  14. Electrochemical behavior of PEDOT/Lignin in Ionic Liquid Electrolytes: Suitable Cathode/Electrolyte System for Sodium Batteries.

    Science.gov (United States)

    Casado, Nerea; Hilder, Matthias; Pozo-Gonzalo, Cristina; Forsyth, Maria; Mecerreyes, David

    2017-02-15

    Biomass derived polymers, such as lignin, contain redox quinone/hydroquinone redox moieties that can be used to store charge. Composites based on the biopolymer lignin and several conjugated polymers have shown good charge storage properties. However, their performance has been just studied in acidic aqueous media limiting the applications mainly to supercapacitors. Here we show that PEDOT/Lignin biopolymers are electroactive in aprotic ionic liquids and we move a step further by assembling sodium full cell batteries using PEDOT/Lignin as electrode material and ionic liquid electrolytes. Thus, the electrochemical activity and cycling of PEDOT/Lignin electrodes is investigated in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (BMPyrFSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) ionic liquid electrolytes. The effects of water and sodium salt addition to the ionic liquids are investigated in order to obtain optimum electrolyte systems for sodium batteries. Finally, sodium batteries based on PEDOT/Lignin cathode with imidazolium based ionic liquid electrolyte showed higher capacity values than pyrrolidinium ones, reaching 70 mAhg-1. Our results demonstrate that PEDOT/Lignin composites can serve as low cost and sustainable cathode materials for sodium batteries.

  15. Corrosion Inhibition of Cast Iron in Arabian Gulf Seawater by Two Different Ionic Liquids

    Directory of Open Access Journals (Sweden)

    El-Sayed M. Sherif

    2015-06-01

    Full Text Available In this paper we report on the corrosion inhibition of cast iron in Arabian Gulf seawater by two different ionic liquids namely, 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl and 1-butyl-1-methylpyrrolidinium chloride ([Py1,4]Cl. The inhibiting influence of the employed ionic liquids was investigated by weight loss, open circuit potential electrochemical impedance spectroscopy, and cyclic potentiodynamic polarization. The results show the corrosion inhibition impact of the employed ionic liquids (ILs. Compared with [Py1,4]Cl, [EMIm]Cl shows a higher inhibition efficiency at a short immersion time, for the examined ILs concentrations. However, [Py1,4]Cl exhibits a higher efficiency upon increasing the immersion time indicating the persistence of the inhibiting influence. The corrosion inhibition of the employed ionic liquids is attributed to the adsorption of the cations of the ionic liquids onto the surface of cast iron forming a corrosion barrier.

  16. Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity.

    Science.gov (United States)

    Oulevey, Patric; Luber, Sandra; Varnholt, Birte; Bürgi, Thomas

    2016-09-19

    Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1-ethyl-3-methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Reactions of Lignin Model Compounds in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-09-15

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

  18. Direct electroplating of copper on tantalum from ionic liquids in high vacuum: origin of the tantalum oxide layer.

    Science.gov (United States)

    Schaltin, Stijn; D'Urzo, Lucia; Zhao, Qiang; Vantomme, André; Plank, Harald; Kothleitner, Gerald; Gspan, Christian; Binnemans, Koen; Fransaer, Jan

    2012-10-21

    In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 °C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.

  19. Fabrication and Characterization of Regenerated Cellulose Films Using Different Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Jin-Hui Pang

    2014-01-01

    Full Text Available The demand for substitution of fossil-based materials by renewable bio-based materials is increasing with the fossil resources reduction and its negative impacts on the environment. In this study, environmentally friendly regenerated cellulose films were successfully prepared using 1-allyl-3-methylimidazolium chloride (AmimCl, 1-butyl-3-methylimidazolium chloride (BmimCl, 1-ethyl-3-methylimidazolium chloride (EmimCl, and 1-ethyl-3-methylimidazolium acetate (EmimAc as solvents, respectively. The results of morphology from scanning electron microscopy (SEM and atomic force microscopy (AFM showed that all the cellulose films possessed smooth, highly uniform, and dense surface. The solid-state cross-polarization/magic angle spinning (CP/MAS 13C NMR spectra and X-ray diffraction (XRD corroborated that the transition from cellulose I to II had occurred after preparation. Moreover, it was shown that the ionic liquid EmimAc possessed much stronger dissolubility for cellulose as compared with other ionic liquids and the cellulose film regenerated from EmimCl exhibited the most excellent tensile strength (119 Mpa. The notable properties of regenerated cellulose films are promising for applications in transparent biodegradable packaging and agricultural purpose as a substitute for PP and PE.

  20. Comparison of different ionic liquids pretreatment for corn stover enzymatic saccharification.

    Science.gov (United States)

    Mood, Sohrab Haghighi; Golfeshan, Amir Hossein; Tabatabaei, Meisam; Abbasalizadeh, Saeed; Ardjmand, Mehdi; Jouzani, Gholamreza Salehi

    2014-01-01

    Recently, application of ionic liquids (ILs) has received much attention due to their special solvency properties as a promising method of pretreatment for lignocellulosic biomass. Easy recovery of ionic liquids, chemical stability, temperature stability, nonflammability, low vapor pressure, and wide liquidus range are among those unique properties. These solvents are also known as green solvents due to their low vapor pressure. The present study was set to compare the effect of five different ILs, namely, 1-ethyl-3-methylimidazolium acetate ([EMIM][Ac]), 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), 1-ethyl-3-methyl imidazolium diethyl phosphate ([EMIM][DEP]), 1-allyl-3-methylimidazolium chloride ([AMIM][Cl]), and 1-ethyl-3-methylimidazolium-hydrogen sulfate ([EMIM][HSO₄]), on corn stover in a bioethanol production process. The performance of ILs was evaluated based on the change observed in chemical structure, crystallinity index, cellulose digestibility, and glucose release. Overall, [EMIM][Ac]-pretreated corn stover led to significantly higher saccharification, with cellulose digestibility reaching 69% after 72 hr, whereas digestibility of untreated barley straw was measured at only 21%.

  1. Phase equilibria of haloalkanes dissolved in ethylsulfate- or ethylsulfonate-based ionic liquids.

    Science.gov (United States)

    Deive, Francisco J; Rodríguez, Ana; Pereiro, Ana B; Shimizu, Karina; Forte, Paulo A S; Romão, Carlos C; Canongia Lopes, José N; Esperança, José M S S; Rebelo, Luís P N

    2010-06-03

    The temperature-composition phase diagrams of 40 binary mixtures composed of a haloalkane dissolved in either 1-ethyl-3-methylimidazolium ethylsulfate or 1-ethyl-3-methylimidazolium ethylsulfonate were measured from ambient temperature to the boiling point temperature of the solute. The coexistence curves corresponding to liquid-liquid equilibria (LLE) boundaries were visually determined and the experimental results have been correlated using either the nonrandom two-liquid (NRTL) model or a set of empirical equations capable of describing the corresponding upper critical solution temperatures (UCSTs) loci. The different types of LLE behavior were discussed in terms of the type of ionic liquid solvent, the alkyl-chain length of the solute, and the type and pattern of halogen substitution present in the haloalkane. Auxiliary simulation data (obtained by ab initio or by molecular dynamics methods) were used to corroborate some of the experimental findings. Also, they correlate in a semiquantitative way the observed LLE behavior with the dipole moments of the different solutes.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. A comparative study of room temperature ionic liquids and their organic solvent mixtures near charged electrodes

    Science.gov (United States)

    Vatamanu, Jenel; Vatamanu, Mihaela; Borodin, Oleg; Bedrov, Dmitry

    2016-11-01

    The structural properties of electrolytes consisting of solutions of ionic liquids in a polar solvent at charged electrode surfaces are investigated using classical atomistic simulations. The studied electrolytes consisted of tetraethylammonium tetrafluoroborate (NEt4-BF4), 1-ethyl-3-methylimidazolium tetrafluoroborate (c2mim-BF4) and 1-octyl-3-methylimidazolium tetrafluoroborate (c8mim-BF4) salts dissolved in acetonitrile solvent. We discuss the influence of electrolyte concentration, chemical structure of the ionic salt, temperature, conducting versus semiconducting nature of the electrode, electrode geometry and surface roughness on the electric double layer structure and capacitance and compare these properties with those obtained for pure room temperature ionic liquids. We show that electrolytes consisting of solutions of ions can behave quite differently from pure ionic liquid electrolytes.

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

    Science.gov (United States)

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

    2015-01-01

    Dialkylcarbonates are viewed as low-cost, low-toxicity reagents, finding application in many areas of green chemistry. Homogeneous alkoxycarbonylation of cellulose was accomplished by applying dialkycarbonates (dimethyl and diethyl carbonate) in the ionic liquid-electrolyte trioctylphosphonium acetate ([P8881 ][OAc])/DMSO or 1-ethyl-3-methylimidazolium acetate ([emim][OAc]). Cellulose dialkylcarbonates with a moderate degree of substitution (DS∼1) are accessible via this procedure and cellulose methylcarbonate was thoroughly characterized for its chemical and physical properties after regeneration. This included HSQC & HMBC NMR, ATR-IR, molecular weight distribution, morphology, thermal properties, and barrier properties after film formation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Complex Structural and Dynamical Interplay of Cyano-Based Ionic Liquids.

    Science.gov (United States)

    Weber, Henry; Kirchner, Barbara

    2016-03-10

    We carried out ab initio molecular dynamics simulations for the three cyano-based ionic liquids, 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1Im][B(CN)4]), 1-ethyl-3-methyl-imidazolium dicyanamide ([C2C1Im][N(CN)2]), and 1-ethyl-3-methylimidazolium thiocyanate ([C2C1Im][SCN]). We found that the [SCN]-based ionic liquid is much more prone to π-π stacking interactions as opposed to the other two ionic liquids, contrary to the fact that all liquids bear the same cation. Hydrogen bonding is strong in the dicyanamide- and the thiocyanate-based ionic liquids and it is almost absent in the tetracyanoborate liquid. The anion prefers to stay on-top of the imidazolium ring with the highest priority for the [N(CN)2](-) anion followed by the [B(CN)4](-) anion. We find that experimental viscosity trends cannot be correlated to the hydrogen bond dynamics which is fastest for [B(CN)4](-) followed by [SCN](-) and [N(CN)2](-). For the dynamics of the cation on-top of itself, we find the order of [B(CN)4](-) followed by [N(CN)2](-) and finally by [SCN](-). Interestingly, this trend correlates well with the viscosity, suggesting a relation between the cation-cation dynamics and the viscosity at least for these cyano-based ionic liquids. These findings, especially the apparent correlation between cation-cation dynamics and the viscosity, might be useful for the suggestion of better ionic liquids in electrolyte applications.

  6. Identification of Structural Motifs of Imidazolium Based Ionic Liquids from Jet-Cooled Infrared Spectroscopy.

    Science.gov (United States)

    Young, Justin W.; Booth, Ryan S.; Annesley, Christopher; Stearns, Jaime A.

    2016-06-01

    Highly variable and potentially revolutionary, ionic liquids (IL) are a class of molecules with potential for numerous Air Force applications such as satellite propulsion, but the complex nature of IL structure and intermolecular interactions makes it difficult to adequately predict structure-property relationships in order to make new IL-based technology a reality. For example, methylation of imidazolium ionic liquids leads to a substantial increase in viscosity but the underlying physical mechanism is not understood. In addition the role of hydrogen bonding in ILs, especially its relationship to macroscopic properties, is a matter of ongoing research. Here, structural motifs are identified from jet-cooled infrared spectra of different imidazolium based ionic liquids, such as 1-ethyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl)imide. Measurements of the C-H stretches indicate three structural families present in the gas phase.

  7. On the Synthesis of Molybdenum Nanoparticles under Reducing Conditions in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Ayi A. Ayi

    2015-01-01

    Full Text Available We report on attempts to synthesize Mo nanoparticles under reducing conditions in ionic liquids (ILs. Ionic liquids were based on the 1-ethyl-3-methylimidazolium or 1-butyl-3-methylimidazolium (Emim and Bmim, resp. cations and the dicyanamide N(CN2, triflate (OTf, bis(trifluoromethylsulfonylimide-(NTf2, tetrafluoroborate (BF4, ethyl sulfate (ES, and methylsulfonate (MS anions. (NH46Mo7O24∗4H2O and NaBH4 were reacted in a set of imidazolium ionic liquids (ILs at 180°C to evaluate the potential of the ILs for stabilization of metallic Mo nanoparticles. XRD and TEM reveal a strong influence of the IL anion on the particle sizes, shapes, and crystal structures. The influence of the IL cation and the reaction temperature is much less pronounced.

  8. Blending municipal solid waste with corn stover for sugar production using ionic liquid process

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Ning [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Xu, Feng [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Sathitsuksanoh, Noppadon [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Thompson, Vicki S. [Idaho National Laboratory (INL), Idaho Falls, ID (United States); Cafferty, Kara [Idaho National Laboratory (INL), Idaho Falls, ID (United States); Li, Chenlin [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Tanjore, Deepti [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Narani, Akash [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pray, Todd R. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Simmons, Blake A. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Singh, Seema [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

    2015-06-01

    Municipal solid waste (MSW) represents an attractive cellulosic resource for sustainable fuel production because of its abundance and its low or perhaps negative cost. However, the significant heterogeneity and toxic contaminants are barriers to efficient conversion to ethanol and other products. In this study, we generated MSW paper mix, blended with corn stover (CS), and have shown that both MSW paper mix alone and MSW/CS blends can be efficiently pretreated in certain ionic liquids (ILs) with high yields of fermentable sugars. After pretreatment in 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]), over 80% glucose has been released with enzymatic saccharification. We have also applied an enzyme free process by adding mineral acid and water directly into the IL/biomass slurry to induce hydrolysis. With the acidolysis process in the IL 1-ethyl-3-methylimidazolium chloride ([C2C1Im]Cl), up to 80% glucose and 90% xylose are released for MSW. The results indicate the feasibility of incorporating MSW as a robust blending agent for biorefineries.

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

    Science.gov (United States)

    Finotello, Alexia; Bara, Jason E; Narayan, Suguna; Camper, Dean; Noble, Richard D

    2008-02-28

    This study focuses on the solubility behaviors of CO2, CH4, and N2 gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) at 40 degrees C and low pressures (approximately 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % [C2mim][BF4] in [C2mim][Tf2N]. Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO2 with N2 or CH4 in pure [C2mim][BF4] can be enhanced by adding 5 mol % [C2mim][Tf2N].

  10. CO2 capture in ionic liquid 1-alkyl-3-methylimidazolium acetate: a concerted mechanism without carbene.

    Science.gov (United States)

    Yan, Fangyong; Dhumal, Nilesh R; Kim, Hyung J

    2017-01-04

    Ionic liquids (ILs) provide a promising medium for CO2 capture. Recently, the family of ILs comprising imidazolium-based cations and acetate anions, such as 1-ethyl-3-methylimidazolium acetate (EMI(+)OAc(-)), has been found to react with CO2 and form carboxylate compounds. N-Heterocyclic carbene (NHC) is widely assumed to be responsible by directly reacting with CO2 though NHC has not been detected in these ILs. Herein, a computational analysis of CO2 capture in EMI(+)OAc(-) is presented. Quantum chemistry calculations predict that NHC is unstable in a polar environment, suggesting that NHC is not formed in EMI(+)OAc(-). Ab initio molecular dynamics simulations indicate that an EMI(+) ion "activated" by the approach of a CO2 molecule can donate its acidic proton to a neighboring OAc(-) anion and form a carboxylate compound with the CO2 molecule. Analysis of this termolecular process indicates that the EMI(+)-to-OAc(-) proton transfer and the formation of 1-ethyl-3-methylimidazolium-2-carboxylate occur essentially concurrently. Based on these findings, a novel concerted mechanism that does not involve NHC is proposed for CO2 capture.

  11. Halogen-Free Phosphonate Ionic Liquids as Precursors of Abrasion Resistant Surface Layers on AZ31B Magnesium Alloy

    Directory of Open Access Journals (Sweden)

    Tulia Espinosa

    2015-01-01

    Full Text Available Surface coatings formed by immersion in the ionic liquids (ILs 1,3-dimethylimidazolium methylphosphonate (LMP101, 1-ethyl-3-methylimidazolium methylphosphonate (LMP102 and 1-ethyl-3-methylimidazolium ethylphosphonate (LEP102 on magnesium alloy AZ31B at 50 °C have been studied. The purpose of increasing the temperature was to reduce the immersion time, from 14 days at room temperature, to 48 hours at 50 °C. The abrasion resistance of the coated alloy was studied by microscratching under progressively increasing load, and compared with that of the uncoated material. The order of abrasion resistance as a function of the IL is LEP102 > LMP101 > LMP102, which is in agreement with the order obtained for the coatings grown at room temperature. The maximum reduction in penetration depth with respect to the uncovered alloy, of a 44.5%, is obtained for the sample treated with the ethylphosphonate LEP102. However, this reduction is lower than that obtained when the coating is grown at room temperature. This is attributed to the increased thickness and lower adhesion of the coatings obtained at 50 °C, particularly those obtained from methylphosphonate ionic liquids. The results are discussed from SEM-EDX and profilometry.

  12. Correlations between phase behaviors and ionic conductivities of (ionic liquid + alcohol) systems

    Energy Technology Data Exchange (ETDEWEB)

    Park, Nam Ku [Division of Chemical Engineering and Molecular Thermodynamics Lab, Hanyang University, Seoul 133-791 (Korea, Republic of); Bae, Young Chan, E-mail: ycbae@hanyang.ac.k [Division of Chemical Engineering and Molecular Thermodynamics Lab, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2010-11-15

    To understand the basic properties of ionic liquids (ILs), we examined the phase behavior and ionic conductivity characteristics using various compositions of different ionic liquids (1-ethyl-3-methylimidazolium hexafluorophosphate [emim; PF6] and 1-benzyl-3-methylimidazolium hexafluorophosphate [bzmim; PF6]) in several different alcohols (ethanol, propanol, 1-butanol, 2-butanol, and hexanol). We conducted a systematic study of the impact of different factors on the phase behavior of imidazolium-based ionic liquids in alcohols. Using a new experimental method with a liquid electrolyte system, we observed that the ionic conductivity of the ionic liquid/alcohol was sensitive to the surrounding temperature. We employed Chang et al.'s thermodynamic model [Chang et al. (1997, 1998) ] based on the lattice model. The obtained co-ordinated unit parameter from this model was used to describe the phase behavior and ionic conductivities of the given system. Good agreement with experimental data of various alcohol and ILs systems was obtained in the range of interest.

  13. Elucidation of the effect of ionic liquid pretreatment on rice husk via structural analyses

    Directory of Open Access Journals (Sweden)

    Ang Teck

    2012-09-01

    Full Text Available Abstract Background In the present study, three ionic liquids, namely 1-butyl-3-methylimidazolium chloride ([BMIM]Cl, 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc, and 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM]DEP, were used to partially dissolve rice husk, after which the cellulose were regenerated by the addition of water. The aim of the investigation is to examine the implications of the ionic liquid pretreatments on rice husk composition and structure. Results From the attenuated total reflectance Fourier transform-infrared (ATR FT-IR spectroscopy, X-ray diffraction (XRD and scanning electron microscopy (SEM results, the regenerated cellulose were more amorphous, less crystalline, and possessed higher structural disruption compared with untreated rice husk. The major component of regenerated cellulose from [BMIM]Cl and [EMIM]DEP pretreatments was cellulose-rich material, while cellulose regenerated from [EMIM]OAc was a matrix of cellulose and lignin. Cellulose regenerated from ionic pretreatments could be saccharified via enzymatic hydrolysis, and resulted in relatively high reducing sugars yields, whereas enzymatic hydrolysis of untreated rice husk did not yield reducing sugars. Rice husk residues generated from the ionic liquid pretreatments had similar chemical composition and amorphousity to that of untreated rice husk, but with varying extent of surface disruption and swelling. Conclusions The structural architecture of the regenerated cellulose and rice husk residues showed that they could be used for subsequent fermentation or derivation of cellulosic compounds. Therefore, ionic liquid pretreatment is an alternative in the pretreatment of lignocellulosic biomass in addition to the conventional chemical pretreatments.

  14. Structural features affecting the enzymatic digestibility of pine wood pretreated with ionic liquids.

    Science.gov (United States)

    Torr, Kirk M; Love, Karen T; Simmons, Blake A; Hill, Stefan J

    2016-03-01

    Pretreating lignocellulosic biomass with certain ionic liquids results in structural and chemical changes that make the biomass more digestible by enzymes. In this study, pine wood was pretreated with 1-ethyl-3-methylimidazolium chloride/acetate ([C2 mim]Cl and [C2 mim][OAc]) at different temperatures to investigate the relative importance of substrate features, such as accessible surface area, cellulose crystallinity, and lignin content, on enzymatic digestibility. The ionic liquid pretreatments resulted in glucan conversions ranging from 23% to 84% on saccharification of the substrates, with [C2 mim][OAc] being more effective than [C2 mim]Cl. The pretreatments resulted in no delignification of the wood, some loss of cellulose crystallinity under certain conditions, and varying levels of increased surface area. Enzymatic digestibility closely correlated with accessible surface area and porosity measurements obtained using Simons' staining and thermoporosimetry techniques. Increased accessible surface area was identified as the principal structural feature responsible for the improved enzymatic digestibility.

  15. Lignin extraction from straw by ionic liquids and enzymatic hydrolysis of the cellulosic residues.

    Science.gov (United States)

    Fu, Dongbao; Mazza, Giuseppe; Tamaki, Yukihiro

    2010-03-10

    Lignocellulose is a promising starting material for bioproducts, ranging from biofuels to specialty chemicals; however, lignocellulose is resistant to enzymatic degradation. Overcoming this resistance is therefore an important priority for the development of the lignocellulosic biorefinery concept. In this work, 1-ethyl-3-methylimidazolium acetate ([emim]Ac) was selected from six ionic liquid candidates for the extraction of lignin from triticale and wheat straw and flax shives. Lignin extractability, composition, and cellulose enzymatic digestibility of the residues after extraction by [emim]Ac were determined at various temperatures (70-150 degrees C) and time intervals (0.5-24 h). The optimal result (52.7% of acid insoluble lignin in triticale straw) was obtained at 150 degrees C after 90 min, yielding >95% cellulose digestibility of the residue. Little cellulose was extracted, and the extracted lignin was recovered by acid precipitation. Selective extraction of lignin by ionic liquids is a potentially efficient technique for the comprehensive utilization of lignocellulose.

  16. Influence of the molecular-oriented structure of ionic liquids on the crystallinity of aluminum hydroxide prepared by a sol-gel process in ionic liquids.

    Science.gov (United States)

    Kinoshita, K; Yanagimoto, H; Suzuki, T; Minami, H

    2015-07-28

    The influence of the structure of ionic liquids on the crystallinity of aluminum hydroxide (Al(OH)3) prepared by a sol-gel process with aluminum isopropoxide (Al(OPr(i))3) in imidazolium-based ionic liquids was investigated. When Al(OH)3 was prepared in ionic liquids having long alkyl chains, such as 1-butyl-3-methylimidazolium salts and 1-methyl-3-octylimidazolium salts, highly crystalline products were obtained. In contrast, Al(OH)3 obtained using the 1-ethyl-3-methylimidazolium salt was an amorphous material, indicating that hydrophobic interaction of the alkyl tail of the imidazolium cation of the ionic liquid strongly affects the crystallinity of sol-gel products and the local structure of the ionic liquid. Moreover, the crystallinity of Al(OH)3 prepared in ionic liquids increased relative to the amount of additional water (ionic liquid/water = 1.28/2.0-3.5/0.2, w/w). In the case of addition of a small amount of water (ionic liquid/water = 3.5/0.2, w/w), the product was amorphous. These results implied that the presence of an ionic liquid and a sufficient amount of water was crucial for the successful synthesis of sol-gel products with high crystallinity. (1)H NMR analyses revealed a shift of the peak associated with the imidazolium cation upon addition of water, which suggested that the molecular orientation of the ionic liquid was similar to that of a micelle.

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

    Directory of Open Access Journals (Sweden)

    Daniel F. Miranda

    2014-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Daniel F.; Urata, Chihiro; Masheder, Benjamin; Dunderdale, Gary J.; Hozumi, Atsushi, E-mail: a.hozumi@aist.go.jp [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98, Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya, Aichi 463-8560 (Japan); Yagihashi, Makoto [Nagoya Municipal Industrial Research Institute, Rokuban, Atsuta-ku, Nagoya 456-0058 (Japan)

    2014-05-01

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

  19. Direct reduction of carbon dioxide to formate in high-gas-capacity ionic liquids at post-transition-metal electrodes.

    Science.gov (United States)

    Watkins, John D; Bocarsly, Andrew B

    2014-01-01

    As an approach to combat the increasing emissions of carbon dioxide in the last 50 years, the sequestration of carbon dioxide gas in ionic liquids has become an attractive research area. Ionic liquids can be made that possess incredibly high molar absorption and specificity characteristics for carbon dioxide. Their high carbon dioxide solubility and specificity combined with their high inherent electrical conductivity also creates an ideal medium for the electrochemical reduction of carbon dioxide. Herein, a lesser studied ionic liquid, 1-ethyl-3-methylimidazolium trifluoroacetate, was used as both an effective carbon dioxide capture material and subsequently as an electrochemical matrix with water for the direct reduction of carbon dioxide into formate at indium, tin, and lead electrodes in good yield (ca. 3 mg h(-1) cm(-2)).

  20. STRUCTURAL CHANGES EVIDENCED BY FTIR SPECTROSCOPY IN CELLULOSE MATERIALS AFTER PRE-TREATMENT WITH IONIC LIQUID AND ENZYMATIC HYDROLYSIS

    Directory of Open Access Journals (Sweden)

    Iuliana Spiridon

    2011-02-01

    Full Text Available Attempts were made to enhance the hydrolysis of Asclepias syriaca (As seed floss and poplar seed floss (PSF by cellulase after pre-treatment with ionic liquids. Two ionic liquids, namely 1-butyl-3-methylimidazolium chloride [BMIM]Cl and 1-ethyl-3-methylimidazolium tetrachloroaluminate [EMIM]Cl-AlCl3, were used. In comparison with conventional cellulose pretreatment processes, the ionic liquids were used under a milder condition corresponding to the optimum activity of cellulase. Hydrolysis kinetics of the IL-treated cellulose materials was significantly enhanced. The initial hydrolysis rates for IL-treated cellulose materials were greater than those of non-treated ones. The structural modifications of hydrolyzed cellulose materials were analyzed using FTIR spectroscopy.

  1. Novel bipyridinium ionic liquids as liquid electrochromic devices.

    Science.gov (United States)

    Jordão, Noémi; Cabrita, Luis; Pina, Fernando; Branco, Luís C

    2014-04-01

    Novel mono and dialkylbipyridinium (viologens) cations combined with iodide, bromide, or bis(trifluoromethanesulfonyl)imide [NTf2] as anions were developed. Selective alkylation synthetic methodologies were optimized in order to obtain the desired salts in moderate to high yields and higher purities. All prepared mono- and dialkylbipyridinium salts were completely characterized by (1)H, (13)C, and (19)F NMR spectroscopy, Fourier-transform IR spectroscopy, and elemental analysis (in the case of NTf2 salts). Melting points, glass transition temperatures by differential scanning calorimetry (DSC) studies, and decomposition temperatures were also checked for different prepared organic salts. Viscosities at specific temperatures and activation energies were determined by rheological studies (including viscosity dependence with temperature in heating and cooling processes). Electrochemical studies based on cyclic voltammetry (CV), differential pulsed voltammetry (DPV), and square-wave voltammetry (SWV) were performed in order to determine the redox potential as well as evaluate reversibility behavior of the novel bipyridinium salts. As proof of concept, we developed a reversible liquid electrochromic device in the form of a U-tube system, the most promising dialkylbipyridinium-NTf2 ionic liquid being used as the electrochromic material and the room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)-imide [EMIM][NTf2], as a stable and efficient electrolyte. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Accelerating rate calorimetry studies of the reactions between ionic liquids and charged lithium ion battery electrode materials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yadong; Dahn, J.R. [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS (Canada); Zaghib, K.; Guerfi, A. [Institut de Recherche d' Hydro-Quebec, 1800 Lionel-Boulet, Varennes, Que. (Canada); Bazito, Fernanda F.C.; Torresi, Roberto M. [Instituto de Quimica Universidade de Sao Paulo, CP 26077, 05513-970 Sao Paulo (Brazil)

    2007-06-30

    Using accelerating rate calorimetry (ARC), the reactivity between six ionic liquids (with and without added LiPF{sub 6}) and charged electrode materials is compared to the reactivity of standard carbonate-based solvents and electrolytes with the same electrode materials. The charged electrode materials used were Li{sub 1}Si, Li{sub 7}Ti{sub 4}O{sub 12} and Li{sub 0.45}CoO{sub 2}. The experiments showed that not all ionic liquids are safer than conventional electrolytes/solvents. Of the six ionic liquids tested, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMI-FSI) shows the worst safety properties, and is much worse than conventional electrolyte. 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI) and 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (Py13-FSI) show similar reactivity to carbonate-based electrolyte. The three ionic liquids 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMI-TFSI), 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide (Pp14-TFSI) and N-trimethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide (TMBA-TFSI) show similar reactivity and are much safer than the conventional carbonate-based electrolyte. A comparison of the reactivity of ionic liquids with common anions and cations shows that ionic liquids with TFSI{sup -} are safer than those with FSI{sup -}, and liquids with EMI{sup +} are worse than those with BMMI{sup +}, Py13{sup +}, Pp14{sup +} and TMBA{sup +}. (author)

  3. Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

    Science.gov (United States)

    Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

    2002-11-01

    The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

  4. Direct electrochemistry and electrocatalysis of hemoglobin in graphene oxide and ionic liquid composite film

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wei, E-mail: swyy26@hotmail.com [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China); Gong, Shixing [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Shi, Fan [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China); Cao, Lili; Ling, Luyang [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Zheng, Weizhe; Wang, Wencheng [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China)

    2014-07-01

    In this paper a novel sensing platform based on graphene oxide (GO), ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate and Nafion for the immobilization of hemoglobin (Hb) was adopted with a carbon ionic liquid electrode (CILE) as the substrate electrode, which was denoted as Nafion/Hb–GO–IL/CILE. Spectroscopic results suggested that Hb molecules were not denatured in the composite. A pair of well-defined redox peaks appeared on the cyclic voltammogram, which was attributed to the realization of direct electron transfer of Hb on the electrode. Electrochemical behaviors of Hb entrapped in the film were carefully investigated by cyclic voltammetry with the electrochemical parameters calculated. Based on the catalytic ability of the immobilized Hb, Nafion/Hb–GO–IL/CILE exhibited excellent electrocatalytic behavior towards the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.01 to 40.0 mM with the detection limit as 3.12 μM (3σ), H{sub 2}O{sub 2} in the concentration range from 0.08 to 635.0 μM with the detection limit as 0.0137 μM (3σ) and NaNO{sub 2} in the concentration range from 0.5 to 800.0 μM with the detection limit as 0.0104 μM (3σ). So the proposed bioelectrode could be served as a new third-generation electrochemical sensor without mediator. - Highlights: • A graphene oxide, 1-ethyl-3-methylimidazolium tetrafluoroborate and hemoglobin composite were prepared. • Composite modified carbon ionic liquid electrode was fabricated. • Direct electrochemistry of hemoglobin was realized on the modified electrode. • Bioelectrocatalytic reduction of the modified electrode to different substrates was studied.

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

    Directory of Open Access Journals (Sweden)

    A. Karmakar

    2014-08-01

    Full Text Available 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.

  6. Enhanced Mixed Feedstock Processing Using Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Simmons, Blake A [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

    2016-10-22

    Biomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before IL pretreatment technology becomes commercially viable. Once of the most significant challenges is the affordable and scalable recovery and recycle or the IL itself. Pervaporation is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration than traditional solvent extraction processes, as well as efficient and energetically more advantageous than standard evaporative techniques. In this study we evaluated a commercially available pervaporation system for IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) that has been proven to be very effective as a biomass pretreatment solvent. We demonstrate that >99.9 wt% [C2C1Im][OAc] can be recovered from aqueous solution and recycled at least five times. A preliminary techno-economic analysis validated the promising role of pervaporation in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses. These findings establish the foundation for further development of pervaporation as an effective method of recovering and recycling ILs using a commercially viable process technology.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cha, E.H. [The Faculty of Liberal Arts (Chemistry), Hoseo University, Asan Choongnam 336-795 (Korea); Lim, S.A. [Functional Proteomics Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea); Park, J.H. [Department of Herbal Medicine, Hoseo University, Asan Choongnam 336-795 (Korea); Kim, D.W. [Department of Chemical Technology, Han Bat National University, Daejon 305-719 (Korea); Macfarlane, D.R. [School of Chemistry, Monash University, Clayton, Vic. 3800 (Australia)

    2008-04-01

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

  8. Physico-Chemical Properties and Phase Behavior of the Ionic Liquid-β-Cyclodextrin Complexes

    Directory of Open Access Journals (Sweden)

    Michał Wlazło

    2013-08-01

    Full Text Available The solubility of β-cyclodextrin (β-CD in ionic liquids (ILs and the activity coefficients at infinite dilution ( of more than 20 solutes (alkanes, aromatic hydrocarbons, alcohols were measured in four chosen ionic liquids, their mixtures with β-CD, and in the β-CD at high temperatures from 338 to 398 K using the inverse gas chromatography. The intermolecular interactions, inclusion complexes and the possible increasing of the solubility of β-CD in water using the IL are presented. The solubility of β-CD in ten chosen hydrophobic ILs at the temperature T = 423 K was detected. The solid-liquid phase diagrams (SLE of {IL (1 + β-CD (2} binary systems at the high mole fraction of the IL were measured for three systems (1-ethyl-3-methylimidazolium chloride, [EMIM][Cl], 1-ethyl-3-methylimidazolium bromide, [EMIM][Br]; and for 1-butyl-3-methylimidazolium chloride, [BMIM][Cl]. The eutectic points were determined at the high IL concentration for all binary systems. The intermolecular interaction and the possibility of inclusion complexes of the IL and/or solvents with β-CD were discussed. The infrared spectroscopy, IR was used for the description of the intermolecular interactions in the (β-CD + IL systems. It was shown via the activity coefficients at infinite dilution results that the inclusion complexes are dependent on the temperature. The addition of β-CD to the IL does not improve the selectivity of the separation of the aliphatics from aromatics.

  9. Long-range magnetic ordering in magnetic ionic liquid: Emim[FeCl{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    De Pedro, I; Rojas, D P; Rodriguez Fernandez, J [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Albo, J; Luis, P; Irabien, A [Departamento de Ingenierioa Quimica y Quimica Inorganica, Universidad de Cantabria, 39005 Santander (Spain); Blanco, Jesus A, E-mail: rodrigufj@unican.e [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2010-07-28

    Up to now most of the magnetic ionic liquids containing tetrachloroferrate ion FeCl{sub 4} have evidenced a paramagnetic temperature dependence of the magnetic susceptibility, with only small deviations from the Curie law at low temperatures. However, we report on the physical properties of 1-ethyl-3-methylimidazolium tetrachloroferrate Emim[FeCl{sub 4}], that clearly shows a long-range antiferromagnetic ordering below the Neel temperature T{sub N{approx}}3.8 K. In addition, the field dependence of the magnetization measured at 2 K is characterized by a linear behaviour up to around 40 kOe, while above this field the magnetization becomes saturated with a value of 4.3 {mu}{sub B}/Fe, which is near the expected fully saturated value of 5 {mu}{sub B}/Fe for an Fe{sup 3+} ion.

  10. Vaporization behavior of tetraoctylphosphonium bis(2-ethylhexyl)phosphate ionic liquid

    Science.gov (United States)

    McMurray, J. W.; Zhou, Y.; Luo, H. M.; Qu, J.

    2017-01-01

    The equilibrium vapor pressures, pe, of the ionic liquid tetraoctylphosphonium bis(2-ethylhexyl)phosphate ([P8888][DEHP]) over the temperature range 409-495 K were determined for the first time using mass loss Knudsen effusion. The pe versus temperature relationship compares well to 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][NTf2]) but is lower than that of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) when measured using the same technique. The discrepancies between the pe determined in this work for [C8mim][NTf2] and [C2mim][NTf2] with previous studies is discussed. The enthalpy and entropy of vaporization for all three fluids are estimated from the Clasius-Clapeyron relation.

  11. Electrochemical behaviour of iron in a third-generation ionic liquid: cyclic voltammetry and micromachining investigations.

    Science.gov (United States)

    Moustafa, Essam M; Mann, Olivier; Fürbeth, Wolfram; Schuster, Rolf

    2009-12-07

    The electrochemical behaviour of Fe in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim](+)Ntf2(-)) and mixtures with Cl(-) is studied with the aim of investigating the applicability of ionic liquids (IL) for the electrochemical machining of iron. Whereas in pure IL iron could not be significantly dissolved, the addition of Cl(-) enables the active dissolution with anodic current densities up to several mA cm(-2). Although several anodic peaks appear in the cyclic voltammograms (CV), the distinct assignment of those electrochemical processes remain difficult. In particular no proof for the formation of FeCl(x) (2-x) complexes during Fe dissolution are deduced from the CV, although such complexes are shown to be stable in the employed electrolyte. In addition, we present electrochemical drilling experiments with short potential pulses, which demonstrate that electrochemical machining of Fe is, in principle, possible in IL based electrolytes, even though hampered by slow machining speed.

  12. Comparison of physical properties of regenerated cellulose films fabricated with different cellulose feedstocks in ionic liquid.

    Science.gov (United States)

    Pang, JinHui; Wu, Miao; Zhang, QiaoHui; Tan, Xin; Xu, Feng; Zhang, XueMing; Sun, RunCang

    2015-05-05

    With the serious "white pollution" resulted from the non-biodegradable plastic films, considerable attention has been directed toward the development of renewable and biodegradable cellulose-based film materials as substitutes of petroleum-derived materials. In this study, environmentally friendly cellulose films were successfully prepared using different celluloses (pine, cotton, bamboo, MCC) as raw materials and ionic liquid 1-ethyl-3-methylimidazolium acetate as a solvent. The SEM and AFM indicated that all cellulose films displayed a homogeneous and smooth surface. In addition, the FT-IR and XRD analysis showed the transition from cellulose I to II was occurred after the dissolution and regeneration process. Furthermore, the cellulose films prepared by cotton linters and pine possessed the most excellent thermal stability and mechanical properties, which were suggested by the highest onset temperature (285°C) and tensile stress (120 MPa), respectively. Their excellent properties of regenerated cellulose films are promising for applications in food packaging and medical materials.

  13. In situ crystallization of ionic liquid [Emim][PF6] from methanol solution under high pressure.

    Science.gov (United States)

    Li, Haining; Su, Lei; Zhu, Xiang; Cheng, Xuerui; Yang, Kun; Yang, Guoqiang

    2014-07-24

    The solubility of 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim][PF6]) in methanol under high pressure is newly measured quantitatively according to the correlation between the ratios of Raman intensity and the concentrations. In situ crystallization and cation conformation of [Emim][PF6] from methanol solution under high pressure have been investigated by using Raman spectroscopy in detail. Remarkably, crystal polymorphism was observed and two crystalline phases (phases I and II) coexisted under high pressure up to ∼ 1.4 GPa. However, only phase II was obtained by recrystallization at ∼ 2 GPa. Our findings may facilitate the development of an effective way for crystallization and purification of ionic liquids under high pressure.

  14. Addition of ammonia and/or oxygen to an ionic liquid for delignification of miscanthus.

    Science.gov (United States)

    Rodríguez, Héctor; Padmanabhan, Sasisanker; Poon, Geoffrey; Prausnitz, John M

    2011-09-01

    Ammonia and/or oxygen were used to enhance the delignification of miscanthus dissolved in 1-ethyl-3-methylimidazolium acetate at 140°C. After dissolution of the gas at 9 bar, water was added as antisolvent to regenerate the dissolved biomass. In a next step, an acetone/water mixture was used to remove carbohydrate-free lignin from the regenerated biomass. The lignin content in the final product was around 10%, much lower than the ca. 23% lignin content of the raw dry miscanthus. This lignin reduction is achieved without diminution of cellulose or of total carbohydrates recovered, relative to the recovery achieved with the ionic liquid pretreatment in contact with air or nitrogen.

  15. Enantioselective toxicities of chiral ionic liquids 1-alkyl-3-methylimidazolium lactate to aquatic algae.

    Science.gov (United States)

    Chen, Hui; Zou, Yuqin; Zhang, Lijuan; Wen, Yuezhong; Liu, Weiping

    2014-09-01

    With the wide application of chiral ionic liquids (CILs) as green solvents, their threats to the aquatic environment cannot be ignored. Thus, risk assessment and the prospective design of inherently safe CILs have become more urgent. However, whether enantioselectivity is a feature of the aquatic toxicity of CILs is poorly understood. Herein, we describe the first investigation into the ecotoxicities of CILs toward green algae Scenedesmus obliquus and Euglena gracilis. A series of methylimidazolium lactic ionic liquids, which cation parts with different alkyl chains and anion part is enantiomers of lactate, are used as representative CILs. The results of S. obliquus showed that the EC50 value of L-(+)-1-ethyl-3-methylimidazolium lactate (L-(+)-EMIM L) was more than 5000 μM, while the EC50 value of D-(-)-1-ethyl-3-methylimidazolium lactate (D-(-)-EMIM L) was 2255.21 μM. Such a distinct difference indicates the enantioselective toxicity of CILs to algae. This enantioselectivity initially persisted with increasing carbon chain length, but no longer exhibited when with greater carbon chain lengths, due to changes in the toxicity weightings of the cation parts. Further research showed that the enantioselective effects of CILs resulted from the differences in the production of reactive oxygen species, the damage to cell membrane integrity and cell wall after exposure to CILs. Results from this study showed that monitoring for the racemate CILs will give an inadequate or misleading environmental risk assessment. Thus, we should improve our ability to predict their effects in natural environments. In the meantime, non-selective use of CILs will do harm to aquatic organisms. Therefore, to minimize their potential for environmental impact, the enantioselective toxicities of CILs with short alkyl chains should be taken into consideration. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. In situ SEM observation of the Si negative electrode reaction in an ionic-liquid-based lithium-ion secondary battery.

    Science.gov (United States)

    Tsuda, Tetsuya; Kanetsuku, Tsukasa; Sano, Teruki; Oshima, Yoshifumi; Ui, Koichi; Yamagata, Masaki; Ishikawa, Masashi; Kuwabata, Susumu

    2015-06-01

    By exploiting characteristics such as negligible vapour pressure and ion-conductive nature of an ionic liquid (IL), we established an in situ scanning electron microscope (SEM) method to observe the electrode reaction in the IL-based Li-ion secondary battery (LIB). When 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide ([C2mim][FSA]) with lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) was used as the electrolyte, the Si negative electrode exhibited a clear morphology change during the charge process, without any solid electrolyte interphase (SEI) layer formation, while in the discharge process, the appearance was slightly changed, suggesting that a morphology change is irreversible in the charge-discharge process. On the other hand, the use of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mim][TFSA]) with Li[TFSA] did not induce a change in the Si negative electrode. It is interesting to note this distinct contrast, which could be attributed to SEI layer formation from the electrochemical breakdown of [C2mim](+) at the Si negative electrode|separator interface in the [C2mim][TFSA]-based LIB. This in situ SEM observation technique could reveal the effect of the IL species electron-microscopically on the Si negative electrode reaction.

  17. Molecular Dynamics Study of Ionic Liquid Film Based on [emim][Tf2N] and [emim][TfO] Adsorbed on Highly Oriented Pyrolytic Graphite

    Institute of Scientific and Technical Information of China (English)

    XUE Xiang-gui; ZHAO Li; L(U) Zhong-yuan; QIAN Hu-iun

    2013-01-01

    Molecular dynamics simulation was used to study the ionic liquid(IL) crystalline film based on 1-ethyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide([emim][Tf2N]) and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate([emim][TfO]) on the graphite surface.Our results show that the cations are parallelly dis-tributed to the surface in the l/2 monolayer(ML) crystalline film.The [Tf2N] anions are parallel to the surface with the oxygen atoms at the bottom,whereas the [TfO] anions are perpendicularly distributed to the surface also with the oxygen atoms at the bottom in the 1/2 ML crystalline film.It has been found that the IL-vapor interface strongly influences the arrangement of ions at the interface.The anions in the top layer with the oxygen atoms outmost turn over to make themselves with the F atoms outmost so as to form C-H...O hydrogen bonds with the cations.The calculated orientational ordering shows that in the outmost layer at the IL-vapor interface,the cation rings present either parallel or perpendicular to the surface at 350 K.

  18. The Influence of Anion Shape on the Electrical Double Layer Microstructure and Capacitance of Ionic Liquids-Based Supercapacitors by Molecular Simulations

    Directory of Open Access Journals (Sweden)

    Ming Chen

    2017-02-01

    Full Text Available Room-temperature ionic liquids (RTILs are an emerging class of electrolytes for supercapacitors. In this work, we investigate the effects of different supercapacitor models and anion shape on the electrical double layers (EDLs of two different RTILs: 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonylimide ([Emim][Tf2N] and 1-ethyl-3-methylimidazolium 2-(cyanopyrrolide ([Emim][CNPyr] by molecular dynamics (MD simulation. The EDL microstructure is represented by number densities of cations and anions, and the potential drop near neutral and charged electrodes reveal that the supercapacitor model with a single electrode has the same EDL structure as the model with two opposite electrodes. Nevertheless, the employment of the one-electrode model without tuning the bulk density of RTILs is more time-saving in contrast to the two-electrode one. With the one-electrode model, our simulation demonstrated that the shapes of anions significantly imposed effects on the microstructure of EDLs. The EDL differential capacitance vs. potential (C-V curves of [Emim][CNPyr] electrolyte exhibit higher differential capacitance at positive potentials. The modeling study provides microscopic insight into the EDLs structure of RTILs with different anion shapes.

  19. Phase behavior and ionic conductivity of concentrated solutions of polystyrene-poly(ethylene oxide) diblock copolymers in an ionic liquid.

    Science.gov (United States)

    Simone, Peter M; Lodge, Timothy P

    2009-12-01

    Concentrated solutions of poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymers were prepared using the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMI][TFSI] as the solvent. The self-assembled microstructures adopted by the copolymer solutions have been characterized using small-angle X-ray scattering. Lyotropic mesophase transitions were observed, with a progression from hexagonally packed cylinders of PEO, to lamellae, to hexagonally packed cylinders of PS upon increasing [EMI][TFSI] content. The change in lamellar domain spacing with ionic liquid concentration was found to be comparable to that reported for other block copolymers in strongly selective solvents. The ionic conductivity of the concentrated PS-PEO/[EMI][TFSI] solutions was measured via impedance spectroscopy, and ranged from 1 x 10(-7) to 1 x 10(-3) S/cm at temperatures from 25 - 100 degrees C. Additionally, the ionic conductivity of the solutions was found to increase with both ionic liquid concentration and molecular weight of the PEO blocks. The ionic conductivity of PEO homopolymer/[EMI][TFSI] solutions was also measured in order to compare the conductivity of the PS-PEO solutions to the expected limit for a lamellar sample with randomly oriented microstructure grains.

  20. Bilayer membrane permeability of ionic liquid-filled block copolymer vesicles in aqueous solution.

    Science.gov (United States)

    Bai, Zhifeng; Zhao, Bin; Lodge, Timothy P

    2012-07-19

    The bilayer membrane permeability of block copolymer vesicles ("polymersomes") with ionic liquid interiors dispersed in water is quantified using fluorescence quenching. Poly((1,2-butadiene)-b-ethylene oxide) (PB-PEO) block copolymer vesicles in water with their interiors filled with a common hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, were prepared containing a hydrophobic dye, Nile Red, by intact migration of dye-encapsulated vesicles from the ionic liquid to water at room temperature. A small quencher molecule, dichloroacetamide, was added to the aqueous solution of the dye-loaded vesicles, and the permeation of the quencher passing through the membrane into the interior was determined from the fluorescence quenching kinetics. Rapid permeation of the quencher across the nanoscale membrane was observed, consistent with the high fluidity of the liquid polybutadiene membrane. Two different PB-PEO copolymers were employed, in order to vary the thickness of the solvophobic membrane. A significant increase in membrane permeability was also observed with decreasing membrane thickness, which is tentatively attributable to differences in quencher solubility in the membranes. Quantitative migration of the vesicles from the aqueous phase back to an ionic liquid phase was achieved upon heating. These microscopically heterogeneous and thermoresponsive vesicles with permeable and robust membranes have potential as recyclable nanoreactors, in which the high viscosity and capital expense of an ionic liquid reaction medium can be mitigated, while retaining the desirable features of ionic liquids as reaction media, and facile catalyst recovery.

  1. Structure of cyano-anion ionic liquids: X-ray scattering and simulations.

    Science.gov (United States)

    Dhungana, Kamal B; Faria, Luiz F O; Wu, Boning; Liang, Min; Ribeiro, Mauro C C; Margulis, Claudio J; Castner, Edward W

    2016-07-14

    Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN(-), SCN(-), N(CN)2 (-), C(CN)3 (-), and B(CN)4 (-). By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4 (-) anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1 (+)/B(CN)4 (-) is cationic.

  2. Are ionic liquids pairwise in gas phase? A cluster approach and in situ IR study.

    Science.gov (United States)

    Dong, Kun; Zhao, Lidong; Wang, Qian; Song, Yuting; Zhang, Suojiang

    2013-04-28

    In this work, we discussed the vaporization and gas species of ionic liquids (ILs) by a cluster approach of quantum statistical thermodynamics proposed by R. Luwig (Phys. Chem. Chem. Phys., 10, 4333), which is a controversial issue up to date. Based on the different sized clusters (2-12 ion-pairs) of the condensed phase, the molar enthalpies of vaporization (ΔvapH, 298.15 K, 1bar) of four representative ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf2]) 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([Emmim][NTf2]) 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) and ethylammonium nitrate ([EtAm][NO3]), were calculated. The predicted ΔvapH were increased remarkably; even the values of [EtAm][NO3] were larger than 700 kJ mol(-1) when the charged isolated ions were assumed to be gas species. However, the ΔvapH were close to experimental measurements when the gas species assumed to be anion-cation pairwise, indicating that the different conformational ion-pairs can coexist in the gas phase when the IL is evaporated. Particularly for the protic IL, [EtAm][NO3], even the neutral precursor molecules by proton transfer can occur in gas phase. In addition, it's found that the effect of hydrogen bonds on the vaporization cannot be negligible by comparing the ΔvapH of [Emim][NTf2] with [Emmim][NTf2]. The in situ and calculated IR spectra provided the further proof that the ions are pairwise in gas phase.

  3. Improved in situ saccharification of cellulose pretreated by dimethyl sulfoxide/ionic liquid using cellulase from a newly isolated Paenibacillus sp. LLZ1.

    Science.gov (United States)

    Hu, Dongxue; Ju, Xin; Li, Liangzhi; Hu, Cuiying; Yan, Lishi; Wu, Tianyun; Fu, Jiaolong; Qin, Ming

    2016-02-01

    A cellulase producing strain was newly isolated from soil samples and identified as Paenibacillus sp. LLZ1. A novel aqueous-dimethyl sulfoxide (DMSO)/1-ethyl-3-methylimidazolium diethyl phosphate ([Emin]DEP)-cellulase system was designed and optimized. In the pretreatment, DMSO was found to be a low-cost substitute of up to 70% ionic liquid to enhance the cellulose dissolution. In the enzymatic saccharification, the optimum pH and temperature of the Paenibacillus sp. LLZ1 cellulase were identified as 6.0 and 40°C, respectively. Under the optimized reaction condition, the conversion of microcrystalline cellulose and bagasse cellulose increased by 39.3% and 37.6%, compared with unpretreated cellulose. Compared to current methods of saccharification, this new approach has several advantages including lower operating temperature, milder pH, and less usage of ionic liquid, indicating a marked progress in environmental friendly hydrolysis of biomass-based materials.

  4. Ionic liquids based on dicyanamide anion: influence of structural variations in cationic structures on ionic conductivity.

    Science.gov (United States)

    Yoshida, Yukihiro; Baba, Osamu; Saito, Gunzi

    2007-05-10

    A series of dicyanamide [N(CN)2]-based ionic liquids were prepared using 1-alkyl-3-methylimidazolium cations with different alkyl chain lengths and ethyl-containing heterocyclic cations with different ring structures, and the influence of such structural variations on their thermal property, density, electrochemical window, viscosity, ionic conductivity, and solvatochromic effects was investigated. We found that the 1,3-dimethylimidazolium salt shows the highest ionic conductivity among ionic liquids free from halogenated anions (3.6 x 10(-2) S cm(-1) at 25 degrees C), and the elongation of the alkyl chain causes the pronounced depression of fluidity and ionic conductivity. Also, such an elongation gives rise to the increase in the degree of ion association in the liquids, mainly caused by the van der Waals interactions between alkyl chains. N(CN)2 salts with 1-ethyl-2-methylpyrazolium (EMP) and N-ethyl-N-methylpyrrolidinium (PY(12)) cations as well as 1-ethyl-3-methylimidazolium (EMI) cation are liquids at room temperature (RT), while the N-ethylthiazolium salt shows a melting event at higher temperature (57 degrees C). Among the three RT ionic liquids with ethyl-containing cations, RT ionic conductivity follows the order EMI > PY(12) > EMP, which does not coincide with the order of fluidity at RT (EMI > EMP > PY(12)). Such a discrepancy is originated from a high degree of ion dissociation in the PY(12) salt, which was manifested in the Walden rule deviation and solvatochromic effects. A series of N(CN)2/C(CN)3 binary mixtures of the EMI salts were also prepared. RT ionic conductivity decreases linearly with increasing the molar fraction of C(CN)3 anion.

  5. Ionic Liquid and HP-β-CD Modified Capillary Zone Electrophoresis to Separate Hyperoside, Luteolin and Chlorogenic Acid

    Institute of Scientific and Technical Information of China (English)

    Yue Ling WANG; Zhong Bo HU; Zhuo Bin YUAN

    2006-01-01

    Ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, 1E-3MI-TFB) and HP-β-CD as modifier was added to the buffer to separate hyperoside, luteolin and chlorogenic acid.Experiments explored the effect of concentration of 1E-3MI-TFB and HP-β-CD on separation.The results indicated that 1.0 mmol/L HP-β-CD and 1‰ (v/v) 1E-3MI-TFB added to the buffer simultaneous y could achieve a good compromise of resolution and analysis time. Capillary experiments and UV spectra indicated that there was interaction between 1E-3MI-TFB and analytes.

  6. Development of an integrated approach for α-pinene recovery and sugar production from loblolly pine using ionic liquids

    DEFF Research Database (Denmark)

    Papa, Gabriella; Kirby, James; Murthy Konda, N. V. S. N.

    2017-01-01

    tissues type of loblolly pine, i.e. pine chips from forest residues (FC), stems from young pine (YW) and lighter wood (LW), while also generating high yields of fermentable sugars following saccharification. We propose that this combined terpene extraction/lignocellulose pretreatment approach may provide......In the southeastern US, loblolly pine (Pinus taeda L.) is widely used as a feedstock in the wood, pulp and paper industry. In loblolly pine, the oleoresin is composed of terpenes and has long been a valuable source for a variety of chemicals, and has recently attracted interest from a biofuel...... perspective for the production of advanced cellulosic biofuels. To date, there have been very few examples where a single conversion process has enabled recovery of both terpenes and fermentable sugars in an integrated fashion. We have used the ionic liquid (IL), 1-ethyl-3-methylimidazolium acetate [C2C1Im...

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

    Directory of Open Access Journals (Sweden)

    Alsu A. Akhmetshina

    2015-12-01

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

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

    Science.gov (United States)

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

    2015-12-30

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

  9. Microwave-Assisted Preparation of CdS Nanoparticles in a Halide-Free Ionic Liquid and Their Photocatalytic Activities

    Institute of Scientific and Technical Information of China (English)

    M. ESMAILI, A; HABIBI-YANGJEH

    2011-01-01

    A microwave-assisted (4-6 min) method was used for the preparation ofCdS nanoparticles in 1-ethyl-3-methylimidazolium ethyl sulfate, a halide-free room-temperature ionic liquid (RTIL). The samples were characterized by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and scanning electron microscopy. Diffuse reflectance spectra showed a 1.33 eV blue shift relative to bulk CdS. The photocatalytic activities of the nanoparticles for photodegradation of methylene blue (MB) using UV and visible light were measured. The photodegradation of MB decreased with calcination temperature. First order rate constants for the reaction under visible and UV irradiations over the nanoparticles prepared in the RTIL rich media were 5.4 and 2.5 higher, respectively, than the sample prepared in water.

  10. Green synthesized nickel nanoparticles modified electrode in ionic liquid medium and its application towards determination of biomolecules.

    Science.gov (United States)

    Babu, Rajendran Suresh; Prabhu, Pandurangan; Narayanan, Sangilimuthu Sriman

    2013-06-15

    An air and moisture stable ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate (EMIMES) was used as an electrolyte for electropolymerization of L-cysteine followed by electrodeposition of nickel nanoparticles (NiNP) on paraffin wax impregnated graphite electrode (PIGE). The electrodeposited NiNP modified electrode showed good redox activity and stability in 0.1M KOH solution. The modified electrode has been characterized using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The modified electrode was examined for electrocatalytic oxidation of some compounds of biological and clinical importance such as vitamin B6, L-tyrosine, L-tryptophan, vanillin, glucose and hydrogen peroxide by cyclic voltammetry to demonstrate the electrocatalytic activity of the electrodeposited NiNPs.

  11. A SAXS study on nanostructure evolution in water free membranes containing ionic liquid: from dry membrane to saturation.

    Science.gov (United States)

    Sekhon, Satpal Singh; Park, Jin-Soo; Choi, Young-Woo

    2010-11-07

    Small-angle X-ray scattering (SAXS) technique has been used to study the evolution of ionomer peak in the recast Nafion membranes containing the ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF(4)). To the best of our knowledge, this is the first report dealing with the study of membranes containing different concentrations of the ionic liquid (EMIBF(4)), from the dry (no ionic liquid) to the saturation (containing 70 wt% ionic liquid) state to understand the evolution of the ionomer peak and the formation of ionic aggregates in these anhydrous membranes. The small-angle scattering maximum (ionomer peak) has been observed to shift continuously toward lower scattering vector (q) values as the ionic liquid content increases. The ionic conductivity behavior for the membranes containing ionic liquid has been found to be closely related with the change of slope of the double logarithmic plot between the reciprocal of the position of the ionomer peak and the polymer weight fraction. The q region over which Porod's law has been obeyed in different membranes was initially narrow and has been observed to widen with an increase in the content of the ionic liquid.

  12. Theoretical investigation of the Te{sub 4}Br{sub 2} molecule in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Elfgen, Roman [Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4+6, 53115, Bonn (Germany); Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45413, Muehlheim an der Ruhr (Germany); Holloczki, Oldamur; Ray, Promit; Kirchner, Barbara [Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4+6, 53115, Bonn (Germany); Groh, Matthias F. [Department of Chemistry and Food Chemistry, Dresden University of Technology, 01062, Dresden (Germany); Ruck, Michael [Department of Chemistry and Food Chemistry, Dresden University of Technology, 01062, Dresden (Germany); Max Planck Institute for Chemical Physics of Solids, Noethnitzer Str. 40, 01187, Dresden (Germany)

    2017-01-15

    Material synthesis in ionic liquids, at or near room temperature, is currently a subject of immense academic interest. In order to illuminate molecular-level details and the underlying chemistry, we carried out molecular simulations of a single Te{sub 4}Br{sub 2} molecule dissolved in the ionic liquid 1-ethyl-3-methylimidazolium chloride, as well as in the ionic liquid mixed with aluminum chloride. Although the ethyl side chain is much too short to show detailed microheterogeneity, significant structuring with the small chloride anions is seen in case of the pure ionic liquid. In the case of the mixture, formation of larger anionic clusters is distinctly observed and analyzed. Due to the tendency of ionic liquids to dissociate, there is a pronounced shift to elongated Te-Br distances in both investigated solvents. However, only in the AlCl{sub 3}-containing liquid, we observe the reaction of the open chain-like Te{sub 4}Br{sub 2} molecule to a closed square-like Te{sub 4}Br{sup +} and AlCl{sub 3}Br{sup -} ion. The molecular arrangement of the [Te{sub 4}]{sup 2+} unit shows negligible deviation from that in the experimental crystal structure. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

    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.

  14. Experimental investigations of an ionic-liquid-based, magnesium ion conducting, polymer gel electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, G.P.; Hashmi, S.A. [Department of Physics and Astrophysics, University of Delhi, Delhi 110007 (India)

    2009-02-15

    Studies on a novel magnesium ion conducting gel polymer electrolyte based on a room temperature ionic liquid (RTIL) is reported. It comprises a Mg-salt, Mg(CF{sub 3}SO{sub 3}){sub 2} [or magnesium triflate, Mg(Tf){sub 2}] solution in an ionic liquid, 1-ethyl-3-methylimidazolium trifluoro-methanesulfonate (EMITf), immobilized with poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP), which is a freestanding, semitransparent and flexible film with excellent mechanical strength. Physical and electrochemical analyses demonstrate promising characteristics of these films, suitable as electrolytes in rechargeable magnesium batteries. The material offers a maximum electrical conductivity of {proportional_to}4.8 x 10{sup -3} S cm{sup -1} at room temperature (20 C) with excellent thermal and electrochemical stabilities. Possible conformational changes in the polymer host PVdF-HFP due to ionic liquid solution entrapment and ion-polymer interaction are investigated by Fourier transform infra-red (FTIR), X-ray diffraction (XRD) and scanning electron microscopic (SEM) methods. The Mg{sup 2+} ion transport in the gel film is confirmed from cyclic voltammetry, impedance and transport number measurements. The Mg{sup 2+} ion transport number (t{sub +}) is {proportional_to}0.26, which indicates a substantial contribution of triflate anion transport along with ionic conduction due to the component ions of the ionic liquid. (author)

  15. Experimental investigations of an ionic-liquid-based, magnesium ion conducting, polymer gel electrolyte

    Science.gov (United States)

    Pandey, G. P.; Hashmi, S. A.

    Studies on a novel magnesium ion conducting gel polymer electrolyte based on a room temperature ionic liquid (RTIL) is reported. It comprises a Mg-salt, Mg(CF 3SO 3) 2 [or magnesium triflate, Mg(Tf) 2] solution in an ionic liquid, 1-ethyl-3-methylimidazolium trifluoro-methanesulfonate (EMITf), immobilized with poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP), which is a freestanding, semitransparent and flexible film with excellent mechanical strength. Physical and electrochemical analyses demonstrate promising characteristics of these films, suitable as electrolytes in rechargeable magnesium batteries. The material offers a maximum electrical conductivity of ∼4.8 × 10 -3 S cm -1 at room temperature (20 °C) with excellent thermal and electrochemical stabilities. Possible conformational changes in the polymer host PVdF-HFP due to ionic liquid solution entrapment and ion-polymer interaction are investigated by Fourier transform infra-red (FTIR), X-ray diffraction (XRD) and scanning electron microscopic (SEM) methods. The Mg 2+ ion transport in the gel film is confirmed from cyclic voltammetry, impedance and transport number measurements. The Mg 2+ ion transport number (t +) is ∼0.26, which indicates a substantial contribution of triflate anion transport along with ionic conduction due to the component ions of the ionic liquid.

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

    Science.gov (United States)

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

    2015-09-01

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

  17. Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

    Science.gov (United States)

    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

  18. Fractionation of sugarcane bagasse using a combined process of dilute acid and ionic liquid treatments.

    Science.gov (United States)

    Diedericks, Danie; van Rensburg, Eugéne; Görgens, Johann F

    2012-08-01

    Biorefineries processing lignocellulose will produce chemicals and fuels from chemical constituents, cellulose, hemicelluloses, and lignin to replace fossil-derived products. Fractionation of sugarcane bagasse into three pure streams of chemical constituents was addressed through dissolution of constituents with the ionic liquids, 1-ethyl-3-methylimidazolium acetate ([EMiM]CH(3)COO) or 1-butyl-3-methylimidazolium methyl sulfate ([BMiM]MeSO(4)). Constituents were isolated from the reaction mixture with the anti-solvents acetone (Ā), acetone-water (AW), and sodium hydroxide (NaOH). Delignification was enhanced by NaOH, although resulting in impure product streams. Xylose pre-extraction (75 % w/w) by dilute acid pretreatment, prior to ionic liquid treatment, improved lignin purity after anti-solvent separation. Fractionation efficiency of the combined process was maximized (84 %) by ionic liquid treatment at 125 °C for 120 min, resulting in 80.2 % (w/w) lignin removal and 76.5 % (w/w) lignin recovery. Ionic liquids achieved similar degrees of delignification, although fully digestible cellulose-rich solids were produced only by [EMiM]CH(3)COO treatment.

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

    Science.gov (United States)

    Murugappan, Krishnan; Silvester, Debbie S

    2016-01-28

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

  20. Capacitance of Ti3C2Tx MXene in ionic liquid electrolyte

    Science.gov (United States)

    Lin, Zifeng; Barbara, Daffos; Taberna, Pierre-Louis; Van Aken, Katherine L.; Anasori, Babak; Gogotsi, Yury; Simon, Patrice

    2016-09-01

    Ti3C2Tx MXene, a two-dimensional (2D) early transition metal carbide, has shown an extremely high volumetric capacitance in aqueous electrolytes, but in a narrow voltage window (less than 1.23 V). The utilization of MXene materials in ionic liquid electrolytes with a large voltage window has never been addressed. Here, we report the preparation of the Ti3C2Tx MXene ionogel film by vacuum filtration for use as supercapacitor electrodes operating in 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) neat ionic liquid electrolyte. Due to the disordered structure of the Ti3C2Tx hydrogel film and a stable spacing after vacuum drying, achieved through ionic liquid electrolyte immersion of the Ti3C2Tx hydrogel film, the Ti3C2Tx surface became accessible to EMI+ and TFSI- ions. A capacitance of 70 F g-1 together with a large voltage window of 3 V was obtained at a scan rate of 20 mV s-1 in neat EMI-TFSI electrolyte. The electrochemical signature indicates a capacitive behavior even at a high scan rate (500 mV s-1) and a high power performance. This work opens up the possibilities of using MXene materials with various ionic liquid electrolytes.

  1. Tuning the theta temperature and critical micellization temperature of polymers in ionic liquids

    Science.gov (United States)

    Lodge, Timothy; Hoarfrost, Megan

    2014-03-01

    Ionic liquids feature a combination of properties that make them very interesting solvents for polymers, but questions remain regarding the thermodynamics of polymer/ionic liquid solutions. In this work, the lower-critical-solution-temperature (LCST) phase behavior of poly(n-butyl methacrylate) (PnBMA) in mixtures of the ionic liquids 1-butyl-3-methylimidazolium: bis(trifluoromethylsulfonyl)imide ([BMIm][TFSI]) and 1-ethyl-3-methylimidazolium:TFSI ([EMIm][TFSI]) is characterized by transmittance, light scattering, and small-angle neutron scattering measurements. Relevant thermodynamic parameters are readily tuned by varying the ionic liquid composition. In particular, the cloud point, spinodal, and theta temperatures are all found to increase linearly with [BMIm] content. The interaction parameters are determined as a function of temperature and concentration using three different methods, and the results from each method are compared. The theta temperatures are then compared quantitatively to the critical micellization temperatures (CMTs) for PnBMA-poly(ethylene oxide) diblocks, to test the proposition that the CMT corresponds to a fixed value of chi.

  2. Engineering ionic liquid-tolerant cellulases for biofuels production.

    Science.gov (United States)

    Wolski, Paul W; Dana, Craig M; Clark, Douglas S; Blanch, Harvey W

    2016-04-01

    Dissolution of lignocellulosic biomass in certain ionic liquids (ILs) can provide an effective pretreatment prior to enzymatic saccharification of cellulose for biofuels production. Toward the goal of combining pretreatment and enzymatic hydrolysis, we evolved enzyme variants of Talaromyces emersonii Cel7A to be more active and stable than wild-type T. emersonii Cel7A or Trichoderma reesei Cel7A in aqueous-IL solutions (up to 43% (w/w) 1,3-dimethylimdazolium dimethylphosphate and 20% (w/w) 1-ethyl-3-methylimidazolium acetate). In general, greater enzyme stability in buffer at elevated temperature corresponded to greater stability in aqueous-ILs. Post-translational modification of the N-terminal glutamine residue to pyroglutamate via glutaminyl cyclase enhanced the stability of T. emersonii Cel7A and variants. Differential scanning calorimetry revealed an increase in melting temperature of 1.9-3.9°C for the variant 1M10 over the wild-type T. emersonii Cel7A in aqueous buffer and in an IL-aqueous mixture. We observed this increase both with and without glutaminyl cyclase treatment of the enzymes.

  3. Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO4

    Directory of Open Access Journals (Sweden)

    Raffaella Mancuso

    2016-07-01

    Full Text Available A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO4 as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis: the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI2 in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et2O.

  4. Characterization of white poplar and eucalyptus after ionic liquid pretreatment as a function of biomass loading using X-ray diffraction and small angle neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Xueming [Beijing Univ. of Chemical Technology (China); Duan, Yonghao [Beijing Univ. of Chemical Technology (China); He, Lilin [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Singh, Seema [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Simmons, Blake [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Cheng, Gang [Beijing Univ. of Chemical Technology (China); Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2017-02-08

    A systematic study was done to understand interactions among biomass loading during ionic liquid (IL) pretreatment, biomass type and biomass structures. White poplar and eucalyptus samples were pretreated using 1-ethyl-3-methylimidazolium acetate (EmimOAc) at 110 °C for 3 h at biomass loadings of 5, 10, 15, 20 and 25 wt%. All of the samples were chemically characterized and tested for enzymatic hydrolysis. Physical structures including biomass crystallinity and porosity were measured by X-ray diffraction (XRD) and small angle neutron scattering (SANS), respectively. SANS detected pores of radii ranging from ~25 to 625 Å, enabling assessment of contributions of pores with different sizes to increased porosity after pretreatment. Contrasting dependences of sugar conversion on white poplar and eucalyptus as a function of biomass loading were observed and cellulose crystalline structure was found to play an important role.

  5. On the interfacial behavior of ionic liquids: surface tensions and contact angles.

    Science.gov (United States)

    Restolho, José; Mata, José L; Saramago, Benilde

    2009-12-01

    In this work the liquid/vapour and the solid/liquid interfaces of a series of ionic liquids: 1-ethyl-3-methylpyridinium ethyl sulfate, [EMPy][EtSO4], 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM][EtSO4], 1-ethanol-3-methylimidazolium tetrafluoroborate, [C2OHMIM][BF4], 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4], and 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF4], were investigated. The surface tension was measured in a wide temperature range, (298-453) K. The contact angles were determined on substrates of different polarities. Both on the polar (glass) and the non-polar substrates ((poly-(tetrafluoroethylene) and poly-(ethylene)), the liquids with maximum and minimum surface tensions lead, respectively, to the highest and the lowest contact angles. The dispersive, gamma(L)(d), and non-dispersive, gamma(L)(nd), components of the liquid surface tension, gamma(L), were calculated from the contact angles on the non-polar substrates using the Fowkes approach. The polarity fraction, gamma(L)(nd)/gamma(L), was compared with the polarity parameter, k, obtained from the fitting of the surface tension vs. temperature data to the Eötvös equation. Good agreement was found for the extreme cases: [OMIM][BF4] exhibits the lowest polarity and [BMIM][BF4], the highest. When compared with the polarity fractions of standard liquids considered as "polar" liquids, the ionic liquids studied may be considered as moderately polar.

  6. Energy properties of an EMI-Im ionic liquid ion source

    Science.gov (United States)

    Lozano, Paulo C.

    2006-01-01

    The identity and the energy distributions of positive and negative ions electrostatically extracted from the liquid phase in an ionic liquid ion source (ILIS) are analysed with a time-of-flight mass spectrometer and a multi-grid retarding potential analyzer. Accurate energy measurements using ionic liquids in an externally wetted configuration are reported for the first time. Droplet-free beams are produced using the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide (EMI-Im) in which the solvated ions (EMI-Im)nEMI+ and (EMI-Im)nIm- with n = 0,1,2 are observed. The small ion source size and the energy distribution widths and deficits of a few electronvolts are quite similar to those of liquid metal ion sources, confirming that ILIS can be used in applications requiring highly focusable beams, e.g. sub-micron ion lithography. Measurements also suggest that solvated ions with n >= 1 exhibit post-extraction fragmentation into lighter species at a rate increasing with their original degree of solvation. About 10% of the total beam current is carried away by metastable species that break up almost immediately after extraction while inside the emitter accelerating region.

  7. Energy properties of an EMI-Im ionic liquid ion source

    Energy Technology Data Exchange (ETDEWEB)

    Lozano, Paulo C [Department of Aeronautics and Astronautics, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Room 37-438, Cambridge, MA 02139 (United States)

    2006-01-07

    The identity and the energy distributions of positive and negative ions electrostatically extracted from the liquid phase in an ionic liquid ion source (ILIS) are analysed with a time-of-flight mass spectrometer and a multi-grid retarding potential analyzer. Accurate energy measurements using ionic liquids in an externally wetted configuration are reported for the first time. Droplet-free beams are produced using the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide (EMI-Im) in which the solvated ions (EMI-Im){sub n}EMI{sup +} and (EMI-Im){sub n}Im{sup -} with n = 0,1,2 are observed. The small ion source size and the energy distribution widths and deficits of a few electronvolts are quite similar to those of liquid metal ion sources, confirming that ILIS can be used in applications requiring highly focusable beams, e.g. sub-micron ion lithography. Measurements also suggest that solvated ions with n {>=} 1 exhibit post-extraction fragmentation into lighter species at a rate increasing with their original degree of solvation. About 10% of the total beam current is carried away by metastable species that break up almost immediately after extraction while inside the emitter accelerating region.

  8. Studies on the Reaction of Iron(II) with NO in a Noncoordinating Ionic Liquid.

    Science.gov (United States)

    Begel, Svetlana; Puchta, Ralph; Sutter, Jörg; Heinemann, Frank W; Dahlenburg, Lutz; Eldik, Rudi van

    2015-07-20

    In an earlier study we investigated the reaction of iron(II) chloride with NO in a strongly coordinating ionic liquid 1-ethyl-3-methylimidazolium dicyanamide [emim][dca] and showed that the actual reactive species in solution was [Fe(II)(dca)5Cl](4-). For the present report we investigated in detail how this reaction could proceed in a noncoordinating ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate [emim][OTf]. The donor ability of OTf(-) is much lower than that of dca(-), such that the solubility of FeCl2 in [emim][OTf] strongly depended on other donors like water or chloride ions present or added to the ionic liquid. On increasing the chloride concentration in [emim][OTf], the tetrachloridoferrate complex [emim]2[FeCl4] was formed, as verified by X-ray crystallography. This complex undergoes reversible binding of NO, for which the UV-vis spectral characteristics of the green-brown nitrosyl product resembled that found for the corresponding nitrosyl complexes formed in water and [emim][dca] as solvents. A detailed analysis of the spectra revealed that the {Fe-NO}(7) species has Fe(II)-NO(•) character in contrast to Fe(III)-NO(-) as found for the other solvents. The formation constant, however, is much higher than in [emim][dca], lying closer to the value found for water as solvent. Surprisingly, the Mössbauer spectrum found in [emim][OTf] is very unusual and unsimilar to that found in water and [emim][dca] as solvents, pointing at a different electron density distribution between Fe and NO in {Fe-NO}.7 First, the high isomer shift points to the presence of iron(II) species in solution, thus indicating that upon NO binding no oxidation to iron(III) occurs. Second, the negligible quadrupole splitting suggests a high local symmetry around the iron center. The nitrosyl product is suggested to be [Fe(II)Cl3NO](-), which is supported by electron paramagnetic resonance (EPR) and IR measurements. The nature of the Fe(II) complexes formed in [emim

  9. Isolation and characterisation of 1-alkyl-3-methylimidazolium chloride ionic liquid-tolerant and biodegrading marine bacteria.

    Directory of Open Access Journals (Sweden)

    Julianne Megaw

    Full Text Available The aim of this study was to isolate and identify marine-derived bacteria which exhibited high tolerance to, and an ability to biodegrade, 1-alkyl-3-methylimidazolium chloride ionic liquids. The salinity and hydrocarbon load of some marine environments may induce selective pressures which enhance the ability of microbes to grow in the presence of these liquid salts. The isolates obtained in this study generally showed a greater ability to grow in the presence of the selected ionic liquids compared to microorganisms described previously, with two marine-derived bacteria, Rhodococcus erythropolis and Brevibacterium sanguinis growing in concentrations exceeding 1 M 1-ethyl-3-methylimidazolium chloride. The ability of these bacteria to degrade the selected ionic liquids was assessed using High Performance Liquid Chromatography (HPLC, and three were shown to degrade the selected ionic liquids by up to 59% over a 63-day test period. These bacterial isolates represent excellent candidates for further potential applications in the bioremediation of ionic liquid-containing waste or following accidental environmental exposure.

  10. Heat capacities of ionic liquids and their heats of solution in molecular liquids

    Energy Technology Data Exchange (ETDEWEB)

    Waliszewski, D. [Department of Physical Chemistry, Univesity of Lodz, PL-90 236 Lodz (Poland); Stepniak, I. [Faculty of Chemical Technology, Poznan University of Technology, PL-60 965 Poznan (Poland); Piekarski, H. [Department of Physical Chemistry, Univesity of Lodz, PL-90 236 Lodz (Poland); Lewandowski, A. [Faculty of Chemical Technology, Poznan University of Technology, PL-60 965 Poznan (Poland)]. E-mail: andrzej.lewandowski@put.poznan.pl

    2005-08-01

    Heat capacities of ionic liquids (IL): 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF{sub 4}), 1-ethyl-3-methyl imidazolium bis((trifluoromethyl)sulfonyl) imide (EMImN(CF{sub 3}SO{sub 2}){sub 2}), 1-bytyl-3-methylimidazolium tetrafluoroborate (BMImBF{sub 4}) and N,N-methyl, propyl pyrrolidinium bis((trifluoromethyl)sulfonyl) imide (MPPyN(CF{sub 3}SO{sub 2}){sub 2}) were measured from 283.15 to 358.15 K. Room temperature heat capacities have also been estimated by an additive group contribution method, based on the assumption that the heat capacity of a molecular compound equals the sum of individual atomic-group contributions. The C {sub p} {sup 293.15K} estimated values are about 12% higher than experimental values. The estimates suggest that heat capacities of ionic liquids do not differ considerably from those typical for molecular liquids (ML). The heats of solution, {delta}{sub sol} H, of ionic liquids EMImBF{sub 4}, BMImBF{sub 4} EMImN(CF{sub 3}SO{sub 2}){sub 2} and MPPyN(CF{sub 3}SO{sub 2}){sub 2} were measured in water, acetonitrile (AN) and methanol, as a function of ionic liquid concentration c {sub m}. The measured {delta}{sub sol} H values decrease with decreasing c {sub m}. Enthalpies of ionic liquid transfer, {delta}{sub t} H deg., from water to methanol and acetonitrile were calculated from measured solution enthalpies. Values of {delta}{sub t} H deg. for the transfer from water to methanol are positive and those for the transfer to acetonitrile are negative.

  11. Combined use of ionic liquid and hydroxypropyl-β-cyclodextrin for the enantioseparation of ten drugs by capillary electrophoresis.

    Science.gov (United States)

    Cui, Yan; Ma, Xiaowei; Zhao, Min; Jiang, Zhen; Xu, Shuying; Guo, Xingjie

    2013-07-01

    In the present study, hydroxypropyl-β-cyclodextrin and an ionic liquid (1-ethyl-3-methylimidazolium-l-lactate) were used as additives in capillary electrophoresis for the enantioseparation of 10 analytes, including ofloxacin, propranolol hydrochloride, dioxopromethazine hydrochloride, isoprenaline hydrochloride, chlorpheniramine maleate, liarozole, tropicamide, amlodipine benzenesulfonate, brompheniramine maleate, and homatropine methylbromide. The effects of ionic liquid concentrations, salt effect, cations, and anions of ionic liquids on enantioseparation were investigated and the results proved that there was a synergistic effect between hydroxypropyl-β-cyclodextrin and the ionic liquid, and the cationic part of the ionic liquid played an important role in the increased resolution. With the developed dual system, all the enantiomers of 10 analytes were well separated in resolutions of 5.35, 1.76, 1.85, 2.48, 2.88, 1.43, 5.45, 4.35, 2.76, and 2.98, respectively. In addition, the proposed method was applied to the determination of the enantiomeric purity of S-ofloxacin after validation of the method in terms of selectivity, repeatability, linearity range, accuracy, precision, limit of detection (LOD), and limit of quality (LOQ).

  12. Antiferromagnetic ordering in magnetic ionic liquid Emim[FeCl{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Pedro, I. de, E-mail: depedrovm@unican.e [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Rojas, D.P. [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, Jesus A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain); Fernandez, J. Rodriguez [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain)

    2011-05-15

    The magnetic ionic liquids (MILs) are considered to open up a wide range of applications because of their magnetic and electrochromic switching. Until recently almost all magnetic ionic liquids containing tetrachloroferrate ion FeCl{sub 4}{sup -} evidenced a paramagnetic temperature dependence of the magnetic susceptibility, with only small deviations from the Curie law at low temperatures. However, 1-ethyl-3-methylimidazolium tetrachloroferrate, Emim[FeCl{sub 4}], clearly exhibits a long-range antiferromagnetic ordering below the Neel temperature T{sub N}{approx}3.8 K. In addition, the shape of the magnetic ordering depends on the cooling speed, indicating that the magnetic coupling could be modified. - Research highlights: Study of MILs is a new and emergent field, involving chemistry, physics, and engineering. MILs have potential applications in relation with their magnetic properties. We present for the first time a long-range magnetic ordering of an ionic liquid. The long-range magnetic ordering depends on the cooling speed.

  13. Spectral insights into gelation microdynamics of PNIPAM in an ionic liquid.

    Science.gov (United States)

    Wang, Zhangwei; Wu, Peiyi

    2011-09-15

    The gelation microdynamic mechanism of PNIPAM in a ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf(2)]), is investigated by FTIR spectroscopy in combination with two-dimensional correlation spectroscopy (2Dcos) and perturbation correlation moving window (PCMW) technique for the first time. Appreciable changes in band frequencies and shapes are observed in the ν(N-H) and ν(C═O) regions, indicating the formation of new interactions between the ionic liquid and PNIPAM and the transformation of interior interaction between polymer chains during gelation. In particular, the variation of the ion environment with the relative change of the isolated and associated components of [C(2)mim][NTf(2)] on the sol-to-gel transition of PNIPAM is revealed by 2DIR analysis to the ν(C-H) region of imidazole ring. Upon cooling, the side chains of PNIPAM experience a changing process from dissociation of the interaction with ionic liquid to formation of N-H···O═C hydrogen bonding, then polymer shrinks from the side chains to backbone, followed by the final immobilization of the associated species in polymer network. Meanwhile, the gelation is actually a desolvation process upon the variation of ion environment.

  14. Lithium-sulphur battery with activated carbon cloth-sulphur cathode and ionic liquid as electrolyte

    Science.gov (United States)

    Swiderska-Mocek, Agnieszka; Rudnicka, Ewelina

    2015-01-01

    In this study a binder-free activated carbon cloth-sulphur (ACC-S) composite cathode is presented. Such a cathode was obtained using the impregnating technique of microporous activated carbon cloth with elemental melted sulphur. The surface morphology of an activated carbon cloth-sulphur electrode was studied using a scanning electron microscope (SEM), which was equipped with an EDX spectroscopy attachment. Electrochemical properties of the ACC-S composite cathode was tested in an ionic liquid electrolyte consisting of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulphonyl)imide (EtMeImNTf2) and bis(trifluoromethanesulphonyl)imide (LiNTf2). The ACC-sulphur cathode working together with lithium anode was tested with the use of cyclic voltammetry (CV), galvanostatic charge/discharge cycles and electrochemical impedance spectroscopy (EIS). The capacity and cyclic stability of the ACC-S composite cathode were much better than those for the sulphur cathode (a mixture of sulphur from graphene nanoplatelets and carbon black) tested in the same ionic liquid electrolyte. The ACC-sulphur cathode showed good cyclability and coulombic efficiency (99%) with the ionic liquid electrolyte. The reversible capacity of the ACC-S|electrolyte|Li cell was ca. 830 mAh g-1 after 50 cycles.

  15. Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

    Science.gov (United States)

    Li, Qin; Ardebili, Haleh

    2016-01-01

    The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

  16. The role of the anion in the toxicity of imidazolium ionic liquids.

    Science.gov (United States)

    Biczak, Robert; Pawłowska, Barbara; Bałczewski, Piotr; Rychter, Piotr

    2014-06-15

    From the environmental protection point of view, the growing interest of ionic liquids in various industrial branches has raised concerns for the toxicity assessment of these compounds. The paper discusses the effect of salts containing the shared 1-ethyl-3-methylimidazolium [EMIM] cation as coupled with five different anions: bromide [Br], nitrate [NO3], p-toluenesulfonate (tosylate) [Ts], dimethylphosphate [dMP] and methanesulfonate [MS] on the growth and development of higher land plants - spring barley and common radish. The experiment was done according to the ISO Standard 11269-2:1995 and the OECD/OCDE Guide 208/2006. As the indications of phytotoxicity, the percentage of sprouts and the level of dry and fresh plant mass were used; in addition, the visual assessment of any signs of damage to the examined plant species, such as growth inhibition and chlorotic changes, was also made. Results of our study has proved the negative impact of ILs on the tested plants and the toxic effect of imidazolium salts was dependent primarily on the applied ionic liquids concentration. The common radish revealed the higher tolerance to the imidazolium as compared to spring barley. The anion type of ionic liquid was crucial for the toxicity against common radish.

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

    Science.gov (United States)

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

    2015-07-28

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

  18. Synthesis and characterization of ionic liquid (EMImBF{sub 4})/Li{sup +} - chitosan membranes for ion battery

    Energy Technology Data Exchange (ETDEWEB)

    Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id [Department of Chemistry, Faculty of Mathematics and Natural Sciences, InstitutTeknologi Bandung, Jl. Ganesha No. 10, Bandung 40132 (Indonesia)

    2015-09-30

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

  19. Measurement of thermal conductivity, viscosity and density of ionic liquid [EMIM][DEP]-based nanofluids☆

    Institute of Scientific and Technical Information of China (English)

    Hua Xie; Zongchang Zhao; Jianhua Zhao; Hongtao Gao

    2016-01-01

    This article studied experimental y the effect of multi-wall carbon nanotubes (MWCNTs) on the thermo physical properties of ionic liquid-based nanofluids. The nanofluids were composed of ionic liquid, 1-ethyl-3-methylimidazolium diethylphosphate [EMIM][DEP], or its aqueous solution[EMIM][DEP](1)+H2O(2) and MWCNTs without any surfactants. The thermal conductivity, viscosity and density of the nanofluids were mea-sured experimental y. The effects of the mass fraction of MWCNTs, temperature and the mole fraction of water on the thermo physical properties of nanofluids were studied. Results show that the thermal conductivity of nanofluids increases within the range of 1.3%–9.7%compared to their base liquids, and have a well linear depen-dence on temperature. The viscosity and density of the nanofluids exhibit a remarkable increase compared with those of the base liquids. Finally, the correlation of the effective thermal conductivity and viscosity of the nanofluids was made using the models in the literatures.

  20. Extraction of lignins from aqueous-ionic liquid mixtures by organic solvents.

    Science.gov (United States)

    Xin, Qin; Pfeiffer, Katie; Prausnitz, John M; Clark, Douglas S; Blanch, Harvey W

    2012-02-01

    The commercial development of ionic liquids (ILs) to pretreat lignocellulose by dissolution of whole biomass and cellulose precipitation by addition of water is hindered by the absence of an effective technique to recover the lignin content of the biomass from the IL. Three organic solvents [ethyl acetate, 1,4-dioxane, and tetrahydrofuran (THF)] were studied for their ability to form a two-liquid-phase system with water and 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]), and for partitioning model lignins and lignin monomers between the two liquid phases. Ternary diagrams were obtained for three [C(2)mim][OAc]/organic solvent/water systems at 22°C. Partition coefficients were measured for several types of lignin in these three systems. Partition coefficients increase with rising water content in the IL phase, and depend strongly on the type of lignin and on the organic solvent. Partition coefficients rise as the pH of the ionic-liquid-rich phase falls. Small molecule model lignin monomer compounds (guaiacol, syringaldehyde) are also readily extracted from the IL/water system by THF. Copyright © 2011 Wiley Periodicals, Inc.

  1. Structural and electrochemical properties of succinonitrile-based gel polymer electrolytes: role of ionic liquid addition.

    Science.gov (United States)

    Suleman, Mohd; Kumar, Yogesh; Hashmi, S A

    2013-06-20

    Experimental studies on the novel compositions of gel polymer electrolytes, comprised of plastic crystal succinonitrile (SN) dispersed with pyrrolidinium and imidazolium-based ionic liquids (ILs) entrapped in a host polymer poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP), are reported. The gel electrolytes are in the form of free-standing films with excellent mechanical, thermal, and electrochemical stability. The introduction of even a small content (~1 wt %) of ionic liquid (1-butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)imide (BMPTFSI) or 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMITf) in the PVdF-HFP/SN system (1:4 w/w) enhances the electrical conductivity by 4 orders of magnitude, that is, from ~10(-7) to ~10(-3) S cm(-1) at room temperature. The structural changes due to the entrapment of SN or SN/ILs mixtures and ion-SN-polymer interactions are examined by Fourier transform infrared (FTIR)/Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and differential scanning calorimmetry (DSC). Various physicochemical properties and fast ion conduction in the gel polymer membranes show their promising characteristics as electrolytes in different ionic devices including supercapacitors.

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

    Science.gov (United States)

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

    2014-12-01

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

  3. Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump-Probe Experiments.

    Science.gov (United States)

    Shin, Jae Yoon; Yamada, Steven A; Fayer, Michael D

    2017-01-11

    Supported ionic liquid membranes (SILMs) are membranes that have ionic liquids impregnated in their pores. SILMs have been proposed for advanced carbon capture materials. Two-dimensional infrared (2D IR) and polarization selective IR pump-probe (PSPP) techniques were used to investigate the dynamics of reorientation and spectral diffusion of the linear triatomic anion, SeCN(-), in poly(ether sulfone) (PES) membranes and room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2). The dynamics in the bulk EmimNTf2 were compared to its dynamics in the SILM samples. Two PES membranes, PES200 and PES30, have pores with average sizes, ∼300 nm and ∼100 nm, respectively. Despite the relatively large pore sizes, the measurements reveal that the reorientation of SeCN(-) and the RTIL structural fluctuations are substantially slower in the SILMs than in the bulk liquid. The complete orientational randomization, slows from 136 ps in the bulk to 513 ps in the PES30. 2D IR measurements yield three time scales for structural spectral diffusion (SSD), that is, the time evolution of the liquid structure. The slowest decay constant increases from 140 ps in the bulk to 504 ps in the PES200 and increases further to 1660 ps in the PES30. The results suggest that changes at the interface propagate out and influence the RTIL structural dynamics even more than a hundred nanometers from the polymer surface. The differences between the IL dynamics in the bulk and in the membranes suggest that studies of bulk RTIL properties may be poor guides to their use in SILMs in carbon capture applications.

  4. True molecular solutions of natural cellulose in the binary ionic liquid-containing solvent mixtures.

    Science.gov (United States)

    Rein, Dmitry M; Khalfin, Rafail; Szekely, Noemi; Cohen, Yachin

    2014-11-04

    Evidence is presented for the first time of true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with ionic liquid. Cryogenic transmission electron microscopy, small-angle neutron-, X-ray- and static light scattering were used to investigate the structure of cellulose solutions in mixture of dimethyl formamide and 1-ethyl-3-methylimidazolium acetate. Structural information on the dissolved chains (average molecular weight ∼ 5 × 10(4)g/mol; gyration radius ∼ 36 nm, persistence length ∼ 4.5 nm), indicate the absence of significant aggregation of the dissolved chains and the calculated value of the second virial coefficient ∼ 2.45 × 10(-2)mol ml/g(2) indicates that this solvent system is a good solvent for cellulose. More facile dissolution of cellulose could be achieved in solvent mixtures that exhibit the highest electrical conductivity. Highly concentrated cellulose solution in pure ionic liquid (27 wt.%) prepared according to novel method, utilizing the rapid evaporation of a volatile co-solvent in binary solvent mixtures at superheated conditions, shows insignificant cellulose molecular aggregation.

  5. Predicting cellulose solvating capabilities of acid-base conjugate ionic liquids.

    Science.gov (United States)

    Parviainen, Arno; King, Alistair W T; Mutikainen, Ilpo; Hummel, Michael; Selg, Christoph; Hauru, Lauri K J; Sixta, Herbert; Kilpeläinen, Ilkka

    2013-11-01

    Different acid-base conjugates were made by combining a range of bases and superbases with acetic and propionic acid. Only the combinations that contained superbases were capable of dissolving cellulose. Proton affinities were calculated for the bases. A range, within which cellulose dissolution occurred, when combined with acetic or propionic acid, was defined for further use. This was above a proton affinity value of about 240 kcal mol(-1) at the MP2/6-311+G(d,p)//MP2/ 6-311+G(d,p) ab initio level. Understanding dissolution allowed us to determine that cation acidity contributed considerably to the ability of ionic liquids to dissolve cellulose and not just the basicity of the anion. By XRD analyses of suitable crystals, hydrogen bonding interactions between anion and cation were found to be the dominant interactions in the crystalline state. From determination of viscosities of these conjugates over a temperature range, certain structures were found to have as low a viscosity as 1-ethyl-3-methylimidazolium acetate, which was reflected in their high rate of cellulose dissolution but not necessarily the quantitative solubility of cellulose in those ionic liquids. 1,5-Diazabicyclo[4.3.0]non-5-enium propionate, which is one of the best structures for cellulose dissolution, was then distilled using laboratory equipment to demonstrate its recyclability.

  6. Parametric study for the optimization of ionic liquid pretreatment of corn stover

    Energy Technology Data Exchange (ETDEWEB)

    Papa, Gabriella [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Feldman, Taya [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Sale, Kenneth L. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Adani, Fabrizio [Univ. degli Studi di Milano (Italy); Singh, Seema [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Simmons, Blake A. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2017-05-30

    A parametric study of the efficacy of the ionic liquid (IL) pretreatment (PT) of corn stover (CS) using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc] ) and cholinium lysinate ([Ch][Lys] ) was conducted. The impact of 50% and 15% biomass loading for milled and non-milled CS on IL-PT was evaluated, as well the impact of 20 and 5 mg enzyme/g glucan on saccharification efficiency. The glucose and xylose released were generated from 32 conditions – 2 ionic liquids (ILs), 2 temperatures, 2 particle sizes (S), 2 solid loadings, and 2 enzyme loadings. Statistical analysis indicates that sugar yields were correlated with lignin and xylan removal and depends on the factors, where S did not explain variation in sugar yields. Both ILs were effective in pretreating large particle sized CS, without compromising sugar yields. The knowledge from material and energy balances is an essential step in directing optimization of sugar recovery at desirable process conditions.

  7. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry

    Science.gov (United States)

    Kruk, D.; Meier, R.; Rachocki, A.; Korpała, A.; Singh, R. K.; Rössler, E. A.

    2014-06-01

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220-258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243-318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258-323 K). The dispersion of 1H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz-20 MHz, and the studies are complemented by 19F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the 1H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the 1H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the 19F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  8. Nanostructured cellulose-xyloglucan blends via ionic liquid/water processing.

    Science.gov (United States)

    Bendaoud, Amine; Kehrbusch, Rene; Baranov, Anton; Duchemin, Benoît; Maigret, Jean Eudes; Falourd, Xavier; Staiger, Mark P; Cathala, Bernard; Lourdin, Denis; Leroy, Eric

    2017-07-15

    In this work, the properties of cellulose (CE)/xyloglucan (XG) biopolymer blends are investigated, taking inspiration from the outstanding mechanical properties of plant cell walls. CE and XG were first co-solubilized in an ionic liquid, 1-ethyl-3-methylimidazolium acetate, in order to blend these biopolymers with a varying CE:XG ratio. The biopolymers were then regenerated together using water to produce solid blends in the form of films. Water-soluble XG persisted in the films following regeneration in water, indicating an attractive interaction between the CE and XG. The final CE:XG ratio of the blends was close to the initial value in solutions, further suggesting that intimate mixing takes place between CE and XG. The resulting CE/XG films were found to be free of ionic liquid, transparent and with no evidence of phase separation at the micron scale. The mechanical properties of the blend with a CE:XG ratio close to one revealed a synergistic effect for which a maximum in the elongation and stress at break was observed in combination with a high elastic modulus. Atomic force microscopy indicates a co-continuous nanostructure for this composition. It is proposed that the non-monotonous variation of the mechanical performance of the films with XG content is due to this observed nanostructuration. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Electrochemical horseradish peroxidase biosensor based on dextran-ionic liquid-V{sub 2}O{sub 5} nanobelt composite material modified carbon ionic liquid electrode

    Energy Technology Data Exchange (ETDEWEB)

    Zhu Zhihong [Institute of Nano-Science and Technology Center, Huazhong Normal University, Wuhan 430079 (China); Sun Xiaoying; Wang Yan [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, 53 Zhenzhou Road, Qingdao 266042 (China); Zeng Yan [Institute of Nano-Science and Technology Center, Huazhong Normal University, Wuhan 430079 (China); Sun Wei, E-mail: sunwei_1975@public.qd.sd.cn [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, 53 Zhenzhou Road, Qingdao 266042 (China); Huang Xintang [Institute of Nano-Science and Technology Center, Huazhong Normal University, Wuhan 430079 (China)

    2010-11-01

    Direct electrochemistry of horseradish peroxidase (HRP) was realized in a dextran (De), 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM]EtOSO{sub 3}) and V{sub 2}O{sub 5} nanobelt composite material modified carbon ionic liquid electrode (CILE). Spectroscopic results indicated that HRP retained its native structure in the composite. A pair of well-defined redox peaks of HRP appeared in pH 3.0 phosphate buffer solution with the formal potential of -0.213 V (vs. SCE), which was the characteristic of HRP heme Fe(III)/Fe(II) redox couple. The result was attributed to the specific characteristics of De-IL-V{sub 2}O{sub 5} nanocomposite and CILE, which promoted the direct electron transfer rate of HRP with electrode. The electrochemical parameters of HRP on the composite modified electrode were calculated and the electrocatalysis of HRP to the reduction of trichloroacetic acid (TCA) was examined. Under the optimal conditions the reduction peak current increased with TCA concentration in the range from 0.4 to 16.0 mmol L{sup -1}. The proposed electrode is valuable for the third-generation electrochemical biosensor.

  10. An Electrochemical NO₂ Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity.

    Science.gov (United States)

    Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

    2015-11-11

    A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity.

  11. A Green Synthesis of Nanosheet-Constructed Pd Particles in an Ionic Liquid and Their Superior Electrocatalytic Performance.

    Science.gov (United States)

    Zhang, Baohua; Xue, Yiguo; Xue, Zhimin; Li, Zhonghao; Hao, Jingcheng

    2015-12-21

    The ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac) is investigated as a solvent for the synthesis of Pd particles. Interestingly, nanosheet-constructed Pd particles could be successfully synthesized in [EMIM]Ac without any additional reducing agent and template under ionothermal conditions. [EMIM]Ac itself works as the solvent, the reducing agent, and the template for the formation of these interesting Pd particles, making this method complementary to the well-known ionic-liquid-precursor approach. Furthermore, [EMIM]Ac can be recycled with no loss of activity for the formation of nanosheet-constructed Pd particles within our studied cycles. Specifically, the nanosheet-constructed Pd particles exhibit superior electrocatalytic activity and stability towards ethanol oxidation and formic acid oxidation compared with commercially available Pd black catalyst, thus demonstrating their promising applications in fuel-cell area. The current approach, thus, presents a green approach towards the synthesis of Pd particles, using only a simple palladium salt and an ionic liquid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

    Directory of Open Access Journals (Sweden)

    Petr Kuberský

    2015-11-01

    Full Text Available A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([EMIM][N(Tf2] showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride (PVDF in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity.

  13. Analysis of SEI formed with cyano-containing imidazolium-based ionic liquid electrolyte in lithium secondary batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Liwei; Yamaki, Jun-ichi [Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-Koen, Kasuga, Fukuoka 816-8580 (Japan); Egashira, Minato [Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi University, 2-16-1, Yamaguchi 755-8611 (Japan)

    2007-12-06

    Two kinds of cyano-containing imidazolium-based ionic liquid, 1-cyanopropyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (CpMI-TFSI) and 1-cyanomethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (CmMI-TFSI), each of which contained 20 wt% dissolved LiTFSI, were used as electrolytes for lithium secondary batteries. Compared with 1-ethyl-3-methylimidazolium-bis(trifluoromethane-sulfonyl)imide (EMI-TFSI) electrolyte, a reversible lithium deposition/dissolution on a stainless-steel working electrode was observed during CV measurements in these cyano-containing electrolytes, which indicated that a passivation layer (solid electrolyte interphase, SEI) was formed during potential scanning. The morphology of the working electrode with each electrolyte system was studied by SEM. Different dentrite forms were found on the electrodes with each electrolyte. The SEI that formed in CpMI-TFSI electrolyte showed the best passivating effect, while the deposited film formed in EMI-TFSI electrolyte showed no passivating effect. The chemical characteristics of the deposited films on the working electrodes were compared by XPS measurements. A component with a cyano group was found in SEIs in CpMI-TFSI and CmMI-TFSI electrolytes. The introduction of a cyano functional group suppressed the decomposition of electrolyte and improved the cathodic stability of the imidazolium-based ionic liquid. The reduction reaction route of imidazolium-based ionic liquid was considered to be different depending on whether or not the molecular structure contained a cyano functional group. (author)

  14. Soft glassy colloidal arrays in an ionic liquid: colloidal glass transition, ionic transport, and structural color in relation to microstructure.

    Science.gov (United States)

    Ueno, Kazuhide; Sano, Yuta; Inaba, Aya; Kondoh, Masashi; Watanabe, Masayoshi

    2010-10-21

    The colloidal glass transition, ionic transport, and optical properties of soft glassy colloidal arrays (SGCAs) that consist of poly(methyl methacrylate) (PMMA)-grafted silica nanoparticles (PMMA-g-NPs) and a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)amide ([C(2)mim][NTf(2)]), were investigated. At lower particle concentrations, PMMA-g-NPs were well-suspended in the IL without any aggregation or sedimentation, and the dilute suspensions showed liquid-like behavior. However, above a certain particle concentration, the suspensions became solidified and exhibited different structural colors depending on the particle concentrations. The liquid-solid transition of the SGCAs was essentially caused by colloidal glass transition. Due to the soft repulsive interaction between the particles, the effective volume fraction of the particle (ϕ(eff)) required for colloidal glass transition was higher than that of the hard sphere system and found to be approximately 0.70-0.74. The SGCA had sufficient ionic conductivity, which was greater than 10(-3) S cm(-1) at room temperature, even in the highly concentrated region. For ionic transport of the cation and the anion in the SGCAs, the decrease in diffusivity observed with the addition of the particles (D(g)/D(0)) was slightly greater for the [NTf(2)] anion than that of the [C(2)mim] cation, suggesting that the [NTf(2)] anion preferentially interacts with the PMMA chains. The SGCAs showed homogeneous, nonbrilliant, and angle-independent structural colors above the glass transition volume fraction. In addition, the color of the SGCAs changed from red to green to blue as the particle concentration increased. A linear relationship was found between the maximum wavelength of the reflection spectra and the center-to-center distance in the SGCAs.

  15. Sugarcane bagasse pretreatment using three imidazolium-based ionic liquids; mass balances and enzyme kinetics

    Directory of Open Access Journals (Sweden)

    Karatzos Sergios

    2012-08-01

    Full Text Available Abstract Background Effective pretreatment is key to achieving high enzymatic saccharification efficiency in processing lignocellulosic biomass to fermentable sugars, biofuels and value-added products. Ionic liquids (ILs, still relatively new class of solvents, are attractive for biomass pretreatment because some demonstrate the rare ability to dissolve all components of lignocellulosic biomass including highly ordered (crystalline cellulose. In the present study, three ILs, 1-butyl-3-methylimidazolium chloride ([C4mim]Cl, 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl, 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc are used to dissolve/pretreat and fractionate sugarcane bagasse. In these IL-based pretreatments the biomass is completely or partially dissolved in ILs at temperatures greater than 130°C and then precipitated by the addition of an antisolvent to the IL biomass mixture. For the first time mass balances of IL-based pretreatments are reported. Such mass balances, along with kinetics data, can be used in process modelling and design. Results Lignin removals of 10% mass of lignin in bagasse with [C4mim]Cl, 50% mass with [C2mim]Cl and 60% mass with [C2mim]OAc, are achieved by limiting the amount of water added as antisolvent to 0.5 water:IL mass ratio thus minimising lignin precipitation. Enzyme saccharification (24 h, 15FPU yields (% cellulose mass in starting bagasse from the recovered solids rank as: [C2mim]OAc(83% > >[C2mim]Cl(53% = [C4mim]Cl(53%. Composition of [C2mim]OAc-treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are characteristic of aqueous alkali pretreatments while those of chloride IL-treated solids resemble aqueous acid pretreatments. All ILs are fully recovered after use (100% mass as determined by ion chromatography. Conclusions In all three ILs regulated addition of water as an antisolvent effected a polysaccharide enriched precipitate since some of the lignin

  16. Cellulose Solubility in Ionic Liquid Mixtures: Temperature, Cosolvent, and Antisolvent Effects.

    Science.gov (United States)

    Minnick, David L; Flores, Raul A; DeStefano, Matthew R; Scurto, Aaron M

    2016-08-18

    Select ionic liquids (ILs) dissolve significant quantities of cellulose through disruption and solvation of inter- and intramolecular hydrogen bonds. In this study, thermodynamic solid-liquid equilibrium was measured with microcrystalline cellulose in a model IL, 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]) and mixtures with protic antisolvents and aprotic cosolvents between 40 and 120 °C. The solubility of cellulose in pure [EMIm][DEP] exhibits an asymptotic maximum of approximately 20 mass % above 100 °C. Solubility studies conducted on antisolvent mixtures with [EMIm][DEP] and [BMIm][Cl] indicate that protic solvents, ethanol, methanol, and water, significantly reduce the cellulose capacity of IL mixtures by 38-100% even at small antisolvent loadings (<5 mass %). Alternatively, IL-aprotic cosolvent (dimethyl sulfoxide, dimethylformamide, and 1,3-dimethyl-2-imidazolidinone) mixtures at mass ratios up to 1:1 enhance cellulose dissolution by 20-60% compared to pure [EMIm][DEP] at select temperatures. Interactions between the IL and molecular solvents were investigated by Kamlet-Taft solvatochromic analysis, FTIR, and NMR spectroscopy. The results indicate that preferential solvation of the IL cation and anion by co- and antisolvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of IL-solvent mixtures.

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

    Science.gov (United States)

    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

  18. Ultrafast Torsional Relaxation of Thioflavin-T in Tris(pentafluoroethyl)trifluorophosphate (FAP) Anion-Based Ionic Liquids.

    Science.gov (United States)

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

    2015-11-01

    Ultrafast spectroscopy on solutes, whose dynamics is very sensitive to the friction in its local environment, has strong potential to report on the microenvironment existing in complex fluids such as ionic liquids. In this work, the torsional relaxation dynamics of Thioflavin-T (ThT), an ultrafast molecular rotor, is investigated in two fluoroalkylphosphate ([FAP])-based ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM][FAP]) and 1-(2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([OHEMIM][FAP]), using ultrafast fluorescence up-conversion spectroscopy. The emission quantum yield and the excited-state fluorescence lifetime measurement suggest that the torsional relaxation of Thioflavin-T, in this class of ionic liquids, is guided by the viscosity of the medium. The temporal profile of the dynamic Stokes' shift of ThT, measured from time-resolved emission spectrum (TRES), displays a multiexponential behavior in both ionic liquids. The long time dynamics of the Stokes' shift is reasonably slower for the hydroxyethyl derivative as compared to the ethyl derivative, which is in accordance with their measured shear viscosity. However, the short time dynamics of Stokes' shift is very similar in both the ionic liquids, and seems to be independent of the measured shear viscosity of the ionic liquid. We rationalize these observations in terms of different locations of ThT in these ionic liquids. These results suggest that despite having a higher bulk viscosity in the ionic liquid, they can provide unique microenvironment in their complex structure, where the reaction can be faster than expected from their measured shear viscosity.

  19. Solubility of Hydrogen Sulfide and Methane in Ionic Liquids: 1-Ethy-3-methylimidazolium Trifluoromethanesulfonate and 1-Butyl-1-methylpyrrolidinium Trifluoromethanesulfonate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Byung-Chul [Hannam University, Seoul (Korea, Republic of)

    2016-04-15

    Solubility data of hydrogen sulfide (H{sub 2}S) and methane (CH{sub 4}) in two kinds of ionic liquids with the same anion: 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][TfO]) and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate ([bmpyr][TfO]) are presented at pressures up to about 30 MPa and at temperatures between 303 K and 343 K. The gas solubilities in ionic liquids were determined by measuring the bubble point pressures of the gas + ionic liquid mixtures with various compositions at different temperatures using a high-pressure equilibrium apparatus equipped with a variable-volume view cell. The H{sub 2}S solubilities in ionic liquid increased with the increase of pressure and decreased with the increase of temperature. On the other hand, the CH{sub 4} solubilities in ionic liquid increased significantly with the increase of pressure, but there was little effect of temperature on the CH{sub 4} solubility. For the ionic liquds [emim][TfO] and [bmpyr][TfO] with the same anion, the solubility of H{sub 2}S as a molality basis was substantially similar, regardless of the temperature and pressure conditions as a molar concentration basis. Comparing the solubilities of H{sub 2}S and CH{sub 4} in the ionic liquid [emim][TfO], the solubilities of H{sub 2}S were much greater than those of CH{sub 4}. For the same type of ionic liquid, the solubility data of H{sub 2}S and CH{sub 4} obtained in this study were compared to the solubility data of CO2 from the literature. When compared at the same pressure and temperature conditions, the CO{sub 2} solubility was in between the solubility of H{sub 2}S and CH{sub 4}.

  20. Vapor pressure of ionic liquids at low temperatures from AC-chip-calorimetry.

    Science.gov (United States)

    Ahrenberg, Mathias; Beck, Martin; Neise, Christin; Keßler, Olaf; Kragl, Udo; Verevkin, Sergey P; Schick, Christoph

    2016-08-03

    The very low vapor pressure of ionic liquids is challenging to measure. At elevated temperatures the liquids might start to decompose, and at relatively low temperatures the vapor pressure becomes too low to be measured by conventional methods. In this work we developed a highly sensitive method for mass loss determination at temperatures starting from 350 K. This technique is based on an alternating current calorimeter equipped with a chip sensor that consists of a free-standing SiNx-membrane (thickness measuring area with lateral dimensions of the order of 1 mm. A small droplet (diameter ca. 600 μm) of an ionic liquid is vaporized isothermally from the chip sensor in a vacuum-chamber. The surface-to-volume-ratio of such a droplet is large and the relative mass loss due to evaporation is therefore easy to monitor by the changing heat capacity (J K(-1)) of the remaining liquid. The vapor pressure is determined from the measured mass loss rates using the Langmuir equation. The method was successfully tested for the determination of the vapor pressure and the vaporization enthalpy of an archetypical ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2]). The data set created in this way in an extremely broad temperature range from 358 K to 780 K has allowed the estimation of the boiling temperature of [EMIm][NTf2]. The value (1120 ± 50) K should be considered as the first reliable boiling point of the archetypical ionic liquid obtained from experimental vapor pressures measured in the most possible close proximity to the normal boiling temperature.

  1. Ratiometric Optical Temperature Sensor Using Two Fluorescent Dyes Dissolved in an Ionic Liquid Encapsulated by Parylene Film

    Directory of Open Access Journals (Sweden)

    Isao Shimoyama

    2013-03-01

    Full Text Available A temperature sensor that uses temperature-sensitive fluorescent dyes is developed. The droplet sensor has a diameter of 40 µm and uses 1 g/L of Rhodamine B (RhB and 0.5 g/L of Rhodamine 110 (Rh110, which are fluorescent dyes that are dissolved in an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate to function as temperature indicators. This ionic liquid is encapsulated using vacuum Parylene film deposition (which is known as the Parylene-on-liquid-deposition (PoLD method. The droplet is sealed by the chemically stable and impermeable Parylene film, which prevents the dye from interacting with the molecules in the solution and keeps the volume and concentration of the fluorescent material fixed. The two fluorescent dyes enable the temperature to be measured ratiometrically such that the droplet sensor can be used in various applications, such as the wireless temperature measurement of microregions. The sensor can measure the temperature of such microregions with an accuracy of 1.9 °C, a precision of 3.7 °C, and a fluorescence intensity change sensitivity of 1.0%/K. The sensor can measure temperatures at different sensor depths in water, ranging from 0 to 850 µm. The droplet sensor is fabricated using microelectromechanical system (MEMS technology and is highly applicable to lab-on-a-chip devices.

  2. Ratiometric optical temperature sensor using two fluorescent dyes dissolved in an ionic liquid encapsulated by Parylene film.

    Science.gov (United States)

    Kan, Tetsuo; Aoki, Hironori; Binh-Khiem, Nguyen; Matsumoto, Kiyoshi; Shimoyama, Isao

    2013-03-27

    A temperature sensor that uses temperature-sensitive fluorescent dyes is developed. The droplet sensor has a diameter of 40 µm and uses 1 g/L of Rhodamine B (RhB) and 0.5 g/L of Rhodamine 110 (Rh110), which are fluorescent dyes that are dissolved in an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate) to function as temperature indicators. This ionic liquid is encapsulated using vacuum Parylene film deposition (which is known as the Parylene-on-liquid-deposition (PoLD) method). The droplet is sealed by the chemically stable and impermeable Parylene film, which prevents the dye from interacting with the molecules in the solution and keeps the volume and concentration of the fluorescent material fixed. The two fluorescent dyes enable the temperature to be measured ratiometrically such that the droplet sensor can be used in various applications, such as the wireless temperature measurement of microregions. The sensor can measure the temperature of such microregions with an accuracy of 1.9 °C, a precision of 3.7 °C, and a fluorescence intensity change sensitivity of 1.0%/K. The sensor can measure temperatures at different sensor depths in water, ranging from 0 to 850 µm. The droplet sensor is fabricated using microelectromechanical system (MEMS) technology and is highly applicable to lab-on-a-chip devices.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  4. Biomass Pretreatment using Ionic Liquid and Glycerol Mixtures

    Science.gov (United States)

    Lynam, Joan Goerss

    Lignocellulosic biomass is a renewable, sustainable resource that can replace or supplement fossil fuels use for liquid fuels and chemicals. However, its recalcitrant structure including interwoven cellulose, hemicelluloses, and lignin biomacromolecules is challenging to deconstruct. Pretreating biomass so that it can be converted to useful liquids dominates process economics. Many pretreatment methods exist, but most require hazardous chemicals or processing conditions. Many ionic liquids (ILs), salts molten below 100°C, can be used to deconstruct lignocellulosic biomass and are less hazardous than the volatile organic compounds typically used. While effective, relatively safe, and recyclable, ILs are expensive. To reduce costs, dilution with other safe compounds is desirable, if there is no impact on deconstruction efficiency. Glycerol, a food additive, is inexpensive and becoming even more so since it is a by-product of the burgeoning biodiesel industry. Use of glycerol as an additive or diluent for ILs is extensively evaluated in this work. Rice hulls are an abundant biomass, with over 100 million tons produced per year, but with little practical use. The IL 1-ethyl-3-methylimidazolium formate ([C2mim][O2CH] or EMIM Form) when mixed with an equal amount of glycerol has been shown to be effective in pretreating rice hulls. Ambient pressure, a pretreatment temperature of 110°C, and a reaction time of three hours produced rice hulls that could be enzymatically hydrolyzed to give reasonably good glucose and xylose yields considering the recalcitrance of this silica-armored biomass. The IL [C2mim][O2CH] was also effective when mixed with an equal amount of glycerol to pretreat loblolly pine, a fast-growing softwood. Loblolly pine was pretreated at 140°C for three hours to produce a solid rich in cellulose and hemicelluloses, while a lignin-rich product could be precipitated from the IL. Similar products were obtained from pretreatment with a mixture of 75% 1

  5. Nanoporous carbon supercapacitors in an ionic liquid: a computer simulation study.

    Science.gov (United States)

    Shim, Youngseon; Kim, Hyung J

    2010-04-27

    Supercapacitors composed of carbon nanotube (CNT) micropores in the room-temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI+BF4(-)) are studied via molecular dynamics (MD)computer simulations. It is found that the distribution of RTIL ions inside the micropore varies significantly with the pore size. Internal solvation of small (6,6) and (7,7) CNTs with an electrified interior wall is effected almost exclusively via counterions. Surprisingly, these counterions, even though they all have the same charge, lead to a charge density characterized by multiple layers with alternating signs. This intriguing feature is attributed to the extended nature of RTIL ion charge distributions, which result in charge separation through preferential orientation inside the electrified nanotubes. In the case of larger (10,10) and (15,15) CNTs, counterions and coions develop multilayer solvation structures. The specific capacitance normalized to the pore surface area is found to increase as the CNT diameter decreases from (15,15) to (7,7). As the pore size further reduces from (6,6) to(5,5), however, the specific capacitance diminishes rapidly. These findings are in excellent agreement with recent experiments with carbon-based materials. A theoretical model based on multiple charge layers is proposed to understand both the MD and experimental results.

  6. Electroless deposition of platinum nanoparticles in room-temperature ionic liquids.

    Science.gov (United States)

    Zhang, Da; Okajima, Takeyoshi; Lu, Dalin; Ohsaka, Takeo

    2013-09-24

    The electroless deposition of Pt nanoparticles (Pt-NPs) could be carried out by dissolving potassium tetrachloroplatinate(II) (K2[PtCl4]) in 1-ethyl-3-methylimidazolium (EMI(+)) room-temperature ionic liquids (RTILs) containing bis(trifluoromethylsulfonyl) imide (NTf2(-)) or tetrafluoroborate (BF4(-)) anion and small cations, such as H(+), K(+), and Li(+). In this case, no deposition of Pt-NPs occurred in RTILs without such small cations. The formation of Pt-NPs was only observed in RTILs containing trifluoromethanesulfonimide (HNTf2) and protons at high temperature (≥80 °C) when potassium hexachloroplatinate(IV) (K2[PtCl6]) was dissolved in the RTILs. The obtained Pt-NPs gave a characteristic absorption spectrum of ultrasmall Pt-NPs. The ultrasmall and uniform Pt-NPs of ca. 1-4 nm in diameter were produced and the Pt-NPs/EMI(+)NTf2(-) dispersion was kept stably for several months without adding any additional stabilizers or capping molecules. The identified Fourier-transform patterns along the [0 1 1] zone axis were observed for the TEM images of Pt-NPs. On the basis of the results obtained, a probable mechanism of the electroless formation of Pt-NPs is discussed.

  7. Antibacterial and Antifungal Activity of Biopolymers Modified with Ionic Liquid and Laponite.

    Science.gov (United States)

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

    2015-09-01

    In the present study, the antimicrobial properties of modified biopolymers such as gelatin and agar have been investigated. These biopolymers (agar and gelatin) are modified by dissolving in ionic liquid (IL) [1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-octyl-3-methyl imidazolium chloride ([C8mim][Cl])] solutions. It was noticed that agar-ionogel (Ag-IL), gelatin-ionogel (GB-IL), and gelatin organogel (gelatin-glycerol solution along with laponite, nanoclay) nanocomposite (GA-NC) formed are highly stable, optically clear, and transparent without any air bubbles. The antimicrobial activity of these (Ag-IL), (GB-IL), and GA-NC were analyzed for both gram-negative (Escherichia coli, Klebsiella pneumoniae) and gram-positive bacterial strains (Staphylococcus aureus and Staphylococcus pyogenes) and fungus A. niger, C. albicans. Antibacterial and antifungal activity studies were carried out at different dilutions such as 100, 99, and 90 % (v/v). It was found that Ag-IL, GB-IL, and individual IL ([C8mim][Cl]) exhibited superior antimicrobial activities, indicating that longer IL chain enhance the cell membrane permeability of S. aureus, S. pyogenes, and E. coli cells. However, GA-NC nanocomposite and [C2mim][Cl]-based composites does not exhibit any bacterial inhibition activity for all bacterial strains.

  8. An aluminum - ionic liquid interface sustaining a durable Al-air battery

    Science.gov (United States)

    Gelman, Danny; Shvartsev, Boris; Wallwater, Itamar; Kozokaro, Shahaf; Fidelsky, Vicky; Sagy, Adi; Oz, Alon; Baltianski, Sioma; Tsur, Yoed; Ein-Eli, Yair

    2017-10-01

    A thorough study of a unique aluminum (Al)-air battery utilizing a pure Al anode, an air cathode, and hydrophilic room temperature ionic liquid electrolyte 1-ethyl-3-methylimidazolium oligofluorohydrogenate [EMIm(HF)2.3F] is reported. The effects of various operation conditions, both at open circuit potential and under discharge modes, on the battery components were discussed. A variety of techniques were utilized to investigate and study the interfaces and processes involved, including electrochemical studies, electron microscopy, spectroscopy and diffraction. As a result of this intensive study, the upon-operation voltage drop (;dip;) obstacle, occurring in the initial stages of the Al-air battery discharge, has been resolved. In addition, the interaction of the Al anode with oligofluorohydrogenate electrolyte forms an Al-O-F layer on the Al surface, which allows both activation and low corrosion rates of the Al anode. The evolution of this layer has been studied via impedance spectroscopy genetic programming enabling a unique model of the Al-air battery.

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

    Science.gov (United States)

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

    2016-07-01

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

  10. Phase diagram, solubility limit and hydrodynamic properties of cellulose in binary solvents with ionic liquid.

    Science.gov (United States)

    Le, Kim Anh; Rudaz, Cyrielle; Budtova, Tatiana

    2014-05-25

    Cellulose solubility phase diagrams in two binary solvents based on 1-ethyl-3-methylimidazolium acetate (EmimAc) mixed with water and with dimethylsulfoxide (DMSO) were built. The minimal amount of EmimAc molecules needed to dissolve cellulose is 2.5-3moles per anhydroglucose unit. This proportion allows calculation of the maximal cellulose concentration soluble in EmimAc-DMSO at any composition; in EmimAc it is around 25-27wt%. Water forms hydrogen bonds with EmimAc and thus competes with cellulose for ionic liquid; the solubility of cellulose in EmimAc-water is much lower than that in EmimAc-DMSO. Hydrodynamic properties of cellulose in two solvent systems were compared. In EmimAc-DMSO cellulose intrinsic viscosity practically does not depend on DMSO content as predicted by the phase diagram. The intrinsic viscosity in EmimAc-water first increases with water content due to cellulose self-aggregation and then abruptly decreases due to coagulation.

  11. Study of surface interactions of ionic liquids with aluminium alloys in corrosion and erosion corrosion processes

    Science.gov (United States)

    Bermúdez, María-Dolores; Jiménez, Ana-Eva; Martínez-Nicolás, Ginés

    2007-06-01

    Surface interactions of alkylimidazolium ionic liquids (ILs) with aluminium alloy Al 2011 have been studied by immersion tests in seven neat ILs [1- n-alkyl-3-methylimidazolium X - (X = BF 4; n = 2 (IL1), 6 (IL2), 8 (IL3). X = CF 3SO 3; n = 2 (IL4). X = (4-CH 3C 6H 4SO 3); n = 2 (IL5). X = PF 6; n = 6 (IL6)] and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (IL7)]. Immersion tests for Al 2011 have also been carried out in 1 wt.% and 5 wt.% solutions of 1-ethyl,3-methylimidazolium tetrafluoroborate (IL1) in water. No corrosion of Al 2011 by neat ILs is observed. The highest corrosion rate for Al 2011 in water is observed in the presence of a 5 wt.% IL1 due to hydrolysis of the anion with hydrogen evolution and formation of aluminium fluoride. Erosion-corrosion processes have been studied for three aluminium alloys (Al 2011, Al 6061 and Al 7075) in a 90 wt.% IL1 solution in water in the presence of α-alumina particles. The erosion-corrosion rates are around 0.2 mm/year or lower, and increase with increasing copper content to give a corrosion resistance order of Al 6061 > Al 7075 > Al 2011. Results are discussed on the basis of scanning electron microscopy (SEM) observations, energy dispersive spectroscopy (EDS) analysis, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) determinations.

  12. A simple recovery process for biodegradable plastics accumulated in cyanobacteria treated with ionic liquids.

    Science.gov (United States)

    Kobayashi, Daigo; Fujita, Kyoko; Nakamura, Nobuhumi; Ohno, Hiroyuki

    2015-02-01

    Here, we proposed a simple recovery process for poly(3-hydroxybutyrate) (PHB) accumulated in cyanobacteria by using ionic liquids (ILs), which dissolve cyanobacteria but not PHB. First, we investigated the effects of IL polarity on hydrogen-bonding receipt ability (β value) and hydrogen-bonding donating ability (α value) and evaluated the subsequent dissolution of cyanobacteria. We found that ILs having α values higher than approximately 0.4 and β values of approximately 0.9 were suitable for dissolution of cyanobacteria. In particular, 1-ethyl-3-methylimidazolium methylphosphonate ([C2mim][MeO(H)PO2]) was found to dissolve cyanobacteria components, but not PHB. Thus, we verified that PHB produced in cyanobacteria could be separated and recovered by simple filtering after dissolution of cyanobacteria in [C2mim][MeO(H)PO2]. Using this technique, more than 98 % of PHB was obtained on the filter as residues separated from cyanobacteria. Furthermore, [C2mim][MeO(H)PO2] maintained the ability to dissolve cyanobacteria after a simple recycling procedure.

  13. Structural features of lignin macromolecules extracted with ionic liquid from poplar wood.

    Science.gov (United States)

    Kim, Jae-Young; Shin, Eun-Jin; Eom, In-Yong; Won, Keehoon; Kim, Yong Hwan; Choi, Donha; Choi, In-Gyu; Choi, Joon Weon

    2011-10-01

    1-Ethyl-3-methylimidazolium acetate ([Emim][CH₃COO]) was used for the extraction of lignin from poplar wood (Populus albaglandulosa), which was called to ionic liquid lignin (ILL) and structural features of ILL were compared with the corresponding milled wood lignin (MWL). Yields of ILL and MWL were 5.8±0.3% and 4.4±0.4%, respectively. The maximum decomposition rate (V(M)) and temperature (T(M)) corresponding to V(M) were 0.25%/ °C and 308.2 °C for ILL and 0.30%/ °C and 381.3 °C for MWL. The amounts of functional groups (OMe and phenolic OH) appeared to be similar for both lignins; approximately 15.5% and 6.7% for ILL and 14.4% and 6.3% for MWL. However, the weight average molecular weight (M(w)) of ILL (6347 Da) was determined to be 2/3-fold of that of MWL (10,002 Da) and polydispersity index (PDI: M(w)/M(n)) suggested that the lignin fragments were more uniform in the ILL (PDI 1.62) than in the MWL (PDI 2.64). Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Ionic liquid-mediated selective extraction of lignin from wood leading to enhanced enzymatic cellulose hydrolysis.

    Science.gov (United States)

    Lee, Sang Hyun; Doherty, Thomas V; Linhardt, Robert J; Dordick, Jonathan S

    2009-04-01

    Lignocellulose represents a key sustainable source of biomass for transformation into biofuels and bio-based products. Unfortunately, lignocellulosic biomass is highly recalcitrant to biotransformation, both microbial and enzymatic, which limits its use and prevents economically viable conversion into value-added products. As a result, effective pretreatment strategies are necessary, which invariably involves high energy processing or results in the degradation of key components of lignocellulose. In this work, the ionic liquid, 1-ethyl-3-methylimidazolium acetate ([Emim][CH3COO]), was used as a pretreatment solvent to extract lignin from wood flour. The cellulose in the pretreated wood flour becomes far less crystalline without undergoing solubilization. When 40% of the lignin was removed, the cellulose crystallinity index dropped below 45, resulting in > 90% of the cellulose in wood flour to be hydrolyzed by Trichoderma viride cellulase. [Emim] [CH3COO] was easily reused, thereby resulting in a highly concentrated solution of chemically unmodified lignin, which may serve as a valuable source of a polyaromatic material as a value-added product.

  15. Ionic Liquid-Based Non-Aqueous Electrolytes for Nickel/Metal Hydride Batteries

    Directory of Open Access Journals (Sweden)

    Tiejun Meng

    2017-02-01

    Full Text Available The voltage of an alkaline electrolyte-based battery is often limited by the narrow electrochemical stability window of water (1.23 V. As an alternative to water, ionic liquid (IL-based electrolyte has been shown to exhibit excellent proton conducting properties and a wide electrochemical stability window, and can be used in proton conducting batteries. In this study, we used IL/acid mixtures to replace the 30 wt % KOH aqueous electrolyte in nickel/metal hydride (Ni/MH batteries, and verified the proton conducting character of these mixtures through electrochemical charge/discharge experiments. Dilution of ILs with acetic acid was found to effectively increase proton conductivity. By using 2 M acetic acid in 1-ethyl-3-methylimidazolium acetate, stable charge/discharge characteristics were obtained, including low charge/discharge overpotentials, a discharge voltage plateau at ~1.2 V, a specific capacity of 161.9 mAh·g−1, and a stable cycling performance for an AB5 metal hydride anode with a (Ni,Co,Zn(OH2 cathode.

  16. Structural and Electronic Properties of Amino Acid Based Ionic Liquids: A Theoretical Study

    Science.gov (United States)

    Wu, Yang; Zhang, Tiantian

    2009-10-01

    The gas-phase ion pairs of the ionic liquids containing 1-ethyl-3-methylimidazolium ([emim]+) and 20 natural amino acids ([AA]-) are studied at the B3LYP/6-311+G (d,p) level. The optimized structures, energies, and natural population analysis are presented and analyzed in terms of their possible correlation with the interaction energies and the H-bond separations. It is found that all the ion pairs of [emim][AA] can form strong H-bond interactions, which are dominated by the side-chain structure and the functional group of amino acid anions. The calculations indicate that an increase of the alkyl side-chain length coincides with a gradual decrease of H-bond energy, while the functional groups lead to the different localized charges on the anions, consequently affecting the electrostatic force. In addition, the intramolecular H bond in [AA]- can weaken the interaction, due to the decrease of the proton-accepting ability of the carbonyl O atoms. The H-bond chemical nature of [emim][AA] is investigated by atoms in molecules and natural bond orbital analyses. The preliminary analysis of 20 kinds of [emim][AA] ion pairs provides some initial hints as to the relationship between the interaction energy and the experimental glass transition temperature.

  17. Study of the Imidazolium-Based Ionic Liquid - ag Electrified Interface on the CO_{2} Electroreduction by Sum Frequency Spectroscopy.

    Science.gov (United States)

    Garcia Rey, Natalia; Dlott, Dana

    2017-06-01

    Imidazolium based ionic liquids (ILs) have been used as a promising system to improve the CO_{2} electroreduction at lower overpotential than other organic or aqueous electrolytes^{1}. Although the detailed mechanism of the CO_{2} electroreduction on Ag has not been elucidated yet, we have developed a methodology to study the electrified interface during the CO_{2} electroreduction using sum frequency generation (SFG) spectroscopy in combination with cyclic voltammetry^{2}. In this work, we tuned the composition of imidazolium-based ILs by exchanging the anion or the functional groups of the imidazolium. We use the nonresonant SFG (NR-SFG) to study the IL-Ag interface and resonant SFG (RES-SFG) to identify the CO adsorbed on the electrode and monitor the Stark shift as a function of cell potential. In previous studies on CO_{2} electroreduction in the IL: 1-ethyl-3-methylimidazolium tetrafluorborate (EMIM-BF_{4}) on Ag, we showed three events occurred at the same potential (-1.33 V vs. Ag/AgCl): the current associated with CO_{2} electroreduction increased, the Stark shift of the adsorbed atop CO doubled in magnitude and the EMIM-BF_{4} underwent a structural transition^{3}. In addition, we also observed how the structural transition of the EMIM-BF_{4} electrolyte shift to lower potentials when the IL is mixed with water. It is known that water enhances the CO_{2} electroreduction producing more CO^{4}. Moreover, the CO is adsorbed in multi-bonded and in atop sites when more water is present in the electrolyte. ^{1}Lau, G. P. S.; Schreier, M.; Vasilyev, D.; Scopelliti, R.; Grätzel, M.; Dyson, P. J., New Insights into the Role of Imidazolium-Based Promoters for the Electroreduction of CO_{2} on a Silver Electrode. J. Am. Chem. Soc. 2016, 138, 7820-7823. ^{2}Garcia Rey, N.; Dlott, D. D., Studies of Electrochemical Interfaces by Broadband Sum Frequency Generation. J. Electroanal. Chem. 2016. DOI:10.1016/j.jelechem.2016.12.023. ^{3}Garcia Rey, N.; Dlott, D. D

  18. Leaching performance of imidazolium based ionic liquids in the presence of hydrogen peroxide for recovery of metals from brass waste

    Energy Technology Data Exchange (ETDEWEB)

    Kelicarslan, A.; Saridede, M. N.

    2016-05-01

    The application of ionic liquids (ILs), 1-methylimidazolium hydrogen sulfate (HmimHSO{sub 4}), 1-ethyl-3-methylimidazolium hydrogen sulfate (EmimHSO{sub 4}) and 1-butyl-3-methylimidazolium chloride (BmimCl) as leaching agents was investigated in the leaching of copper and zinc from brass waste in the presence of an oxidant, hydrogen peroxide (H{sub 2}O{sub 2}). Factors that affect copper and zinc dissolution rates such as ionic liquid concentration, time and temperature were investigated. The results indicated that zinc was dissolved in leach solutions with EmimHSO{sub 4} and HmimHSO{sub 4}, completely. Temperature had no considerable influence on copper dissolution rate whilst the rate increased with decreasing IL concentration. In the EmimHSO{sub 4} system, higher copper recoveries were achieved with 40% and 60% IL concentrations compared with IL concentrations of 20% and 80% at 40 degree centigrade leaching temperature. Copper dissolution rates decreased with EmimHSO{sub 4} concentration at 60 degree centigrade and 80 degree centigrade in the following order; 40%>20%>60%>80%. On the other hand the leaching system with BmimCl generally resulted in poor extractions of copper and zinc. (Author)

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

    Science.gov (United States)

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

    2016-02-28

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

  20. Monoenergetic source of kilodalton ions from Taylor cones of ionic liquids

    Science.gov (United States)

    Larriba, C.; Castro, S.; Fernandez de la Mora, J.; Lozano, P.

    2007-04-01

    The ionic liquid ion sources (ILISs) recently introduced by Lozano and Martinez Sanchez [J. Colloid Interface Sci. 282, 415 (2005)], based on electrochemically etched tungsten tips as emitters for Taylor cones of ionic liquids (ILs), have been tested with ionic liquids [A+B-] of increasing molecular weight and viscosity. These ILs have electrical conductivities well below 1S/m and were previously thought to be unsuitable to operate in the purely ionic regime because their Taylor cones produce mostly charged drops from conventional capillary tube sources. Strikingly, all the ILs tried on ILIS form charged beams composed exclusively of small ions and cluster ions A+(AB)n or B-(AB)n, with abundances generally peaking at n =1. Particularly interesting are the positive and negative ion beams produced from the room temperature molten salts 1-methyl-3-pentylimidazolium tris(pentafluoroethyl) trifluorophosphate (C5MI-(C2F5)3PF3) and 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) sulfonylimide (EMI-(C2F5SO3)2N). We extend to these heavier species the previous conclusions from Lozano and Martinez Sanchez on the narrow energy distributions of the ion beams. In combination with suitable ILs, this source yields nanoamphere currents of positive and negative monoenergetic molecular ions with masses exceeding 2000amu. Potential applications are in biological secondary ion mass spectrometry, chemically assisted high-resolution ion beam etching, and electrical propulsion. Advantages of the ILISs versus similar liquid metal ion sources include the possibility to form negative as well as positive ion beams and a much wider range of ion compositions and molecular masses.

  1. Size Control and Fractionation of Ionic Liquid Filled Polymersomes with Glassy and Rubbery Bilayer Membranes.

    Science.gov (United States)

    So, Soonyong; Lodge, Timothy P

    2016-05-17

    We demonstrate control over the size of ionic liquid (IL) filled polymeric vesicles (polymersomes) by three distinct methods: mechanical extrusion, cosolvent-based processing in an IL, and fractionation of polymersomes in a biphasic system of IL and water. For the representative ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([EMIM][TFSI])), the size and dispersity of polymersomes formed from 1,2-polybutadiene-b-poly(ethylene oxide) (PB-PEO) and polystyrene-b-poly(ethylene oxide) (PS-PEO) diblock copolymers were shown to be sensitive to assembly conditions. During mechanical extrusion through a polycarbonate membrane, the relatively larger polymersomes were broken up and reorganized into vesicles with mean size comparable to the membrane pore (100 nm radius); the distribution width also decreased significantly after only a few passes. Other routes were studied using the solvent-switch or cosolvent (CS) method, whereby the initial content of the cosolvent and the PEO block length of PS-PEO were systemically changed. The nonvolatility of the ionic liquid directly led to the desired concentration of polymersomes in the ionic liquid using a single step, without the dialysis conventionally used in aqueous systems, and the mean vesicle size depended on the amount of cosolvent employed. Finally, selective phase transfer of PS-PEO polymersomes based on size was used to extract larger polymersomes from the IL to the aqueous phase via interfacial tension controlled phase transfer. The interfacial tension between the PS membrane and the aqueous phase was varied with the concentration of sodium chloride (NaCl) in the aqueous phase; then the larger polymersomes were selectively separated to the aqueous phase due to differences in shielding of the hydrophobic core (PS) coverage by the hydrophilic corona brush (PEO). This novel fractionation is a simple separation process without any special apparatus and can help to prepare monodisperse polymersomes

  2. Hybrid electrolytes based on ionic liquids and amorphous porous silicon nanoparticles: Organization and electrochemical properties

    KAUST Repository

    Tchalala, Mohammed

    2017-05-06

    Ionic liquids (ILs) and ionic liquid-nanoparticle (IL-NP) hybrid electrolytes have garnered a lot of interest due to their unique properties that stimulate their use in various applications. Herein, we investigate the electrochemical and photo-physical properties of organic-inorganic hybrid electrolytes based on three imidazolium-based ionic liquids, i.e., 1-buthyl-3-methylimidazolium thiocyanate ([bmim] [SCN]), 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim] [BF4]) and 1-buthyl-3-methylimidazolium acetate ([bmim] [Ac]) that are covalently tethered to amorphous porous silicon nanoparticles (ap-Si NPs). We found that the addition of ap-Si NPs confer to the ILs a pronounced boost in the electrocatalytic activity, and in mixtures of ap-Si NPs and [bmim] [SCN], the room-temperature current transport is enhanced by more than 5 times compared to bare [bmim] [SCN]. A detailed structural investigation by transmission electron microscope (TEM) showed that the ap-Si NPs were well dispersed, stabilized and highly aggregated in [bmim] [SCN], [emim] [BF4] and [bmim] [Ac] ILs, respectively. These observations correlate well with the enhanced current transport observed in ap-Si NPs/[bmim] [SCN] evidenced by electrochemical measurements. We interpreted these observations by the use of UV–vis absorbance, photoluminescence (PL), FTIR and solid-state NMR spectroscopy. We found that the ap-Si NPs/[bmim] [SCN] hybrid stands out due to its stability and optical transparency. This behavior is attributed to the iron(III) thiocyanate complexion as per the experimental findings. Furthermore, we found that the addition of NPs to [emim] [BF4] alters the equilibrium of the IL, which consequently improved the stability of the NPs through intermolecular interactions with the two ionic layers (anionic and cationic layers) of the IL. While in the case of [bmim] [Ac], the dispersion of ap-Si NPs was restrained because of the high viscosity of this IL.

  3. Improved activity of a thermophilic cellulase, Cel5A, from Thermotoga maritima on ionic liquid pretreated switchgrass.

    Directory of Open Access Journals (Sweden)

    Zhiwei Chen

    Full Text Available Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc] pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25-42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding.

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

    Energy Technology Data Exchange (ETDEWEB)

    Espinosa, Tulia; Sanes, José; Jiménez, Ana-Eva [Grupo de Ciencia de Materiales e Ingeniería Metalúrgica, Departamento de Ingeniería de Materiales y Fabricación, Universidad Politécnica de Cartagena, Campus de la Muralla del Mar. C/Doctor Fleming, s/n. 30202-Cartagena (Spain); Bermúdez, María-Dolores, E-mail: mdolores.bermudez@upct.es [Grupo de Ciencia de Materiales e Ingeniería Metalúrgica, Departamento de Ingeniería de Materiales y Fabricación, Universidad Politécnica de Cartagena, Campus de la Muralla del Mar. C/Doctor Fleming, s/n. 30202-Cartagena (Spain)

    2013-05-15

    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]EtPO{sub 3}H); 1-ethyl-3-methylimidazolium octylsulfate ([EMIM]C{sub 8}H{sub 17}SO{sub 4}); 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM]BF{sub 4}) and 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF{sub 6}). 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]C{sub 8}H{sub 17}SO{sub 4} reacts with copper to form the corresponding copper sulphate salt. [EMIM]EtPO{sub 3}H produces severe corrosion to form a phosphonate–copper soluble phase. [HMIM]BF{sub 4} gives rise to the highest roughness increase of the

  5. 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.

    Science.gov (United States)

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

    2015-12-03

    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.

  6. Pressure effects on Emim[FeCl4], a magnetic ionic liquid with three-dimensional magnetic ordering.

    Science.gov (United States)

    García-Saiz, Abel; de Pedro, Imanol; Blanco, Jesús A; González, Jesús; Rodríguez Fernández, Jesús

    2013-03-21

    We report a combined study using magnetization and Raman spectroscopy on the magnetic ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate, Emim[FeCl4]. This material shows a long-range antiferromagnetic ordering below the Néel temperature T(N) ≈ 3.8 K. The effects of pressure on the magnetic properties have been studied using a miniature piston-cylinder CuBe pressure cell. This three-dimensional ordering is strongly influenced when hydrostatic pressure is applied. It is observed that low applied pressure is enough to modify the magnetic interactions, inducing a transition from antiferromagnetic to ferrimagnetic ordering. Raman spectroscopy measurements reveal important information about the existence of isolated [FeCl4](-) anions and the absence of dimeric [Fe2Cl7](-) units in the liquid and solid states. These features seem to suggest that the superexchange pathways responsible for the appearance of magnetic ordering are mediated through Fe-Cl-Cl-Fe. Furthermore, the liquid-solid phase transition exhibits a magnetic hysteresis near room temperature, which can be tuned by weak pressures.

  7. Ionic-liquid-assisted microwave distillation coupled with headspace single-drop microextraction followed by GC-MS for the rapid analysis of essential oil in Dryopteris fragrans.

    Science.gov (United States)

    Jiao, Jiao; Gai, Qing-Yan; Wang, Wei; Luo, Meng; Zhao, Chun-Jian; Fu, Yu-Jie; Ma, Wei

    2013-12-01

    A rapid, green and effective miniaturized sample preparation technique, ionic-liquid-assisted microwave distillation coupled with headspace single-drop microextraction was developed for the extraction of essential oil from dried Dryopteris fragrans. 1-Ethyl-3-methylimidazolium acetate was the optimal ionic liquid as the destruction agent of plant cell walls and microwave absorption was medium. n-Heptadecane (2.0 μL) was adopted as the suspended microdrop solvent in the headspace for the extraction and concentration of essential oil. The optimal parameters of the proposed method were an irradiation power of 300 W, sample mass of 0.9 g, mass ratio of ionic liquids to sample of 2.8, extraction temperature of 79°C, and extraction time of 3.6 min. In comparison to the previous reports, the proposed technique could equally monitor all the essential oil components with no significant differences in a simple way, which was more rapid and required a much lower amount of sample. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2015-12-03

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

  9. Nano-Structural Investigation on Cellulose Highly Dissolved in Ionic Liquid: A Small Angle X-ray Scattering Study

    Directory of Open Access Journals (Sweden)

    Takatsugu Endo

    2017-01-01

    Full Text Available We investigated nano-structural changes of cellulose dissolved in 1-ethyl-3-methylimidazolium acetate—an ionic liquid (IL—using a small angle X-ray scattering (SAXS technique over the entire concentration range (0–100 mol %. Fibril structures of cellulose disappeared at 40 mol % of cellulose, which is a significantly higher concentration than the maximum concentration of dissolution (24–28 mol % previously determined in this IL. This behavior is explained by the presence of the anion bridging, whereby an anion prefers to interact with multiple OH groups of different cellulose molecules at high concentrations, discovered in our recent work. Furthermore, we observed the emergence of two aggregated nano-structures in the concentration range of 30–80 mol %. The diameter of one structure was 12–20 nm, dependent on concentration, which is ascribed to cellulose chain entanglement. In contrast, the other with 4.1 nm diameter exhibited concentration independence and is reminiscent of a cellulose microfibril, reflecting the occurrence of nanofibrillation. These results contribute to an understanding of the dissolution mechanism of cellulose in ILs. Finally, we unexpectedly proposed a novel cellulose/IL composite: the cellulose/IL mixtures of 30–50 mol % that possess liquid crystallinity are sufficiently hard to be moldable.

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

    Science.gov (United States)

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

    2015-04-02

    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.

  11. The general phase behavior of mixtures of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide ionic liquids with n-alkyl alcohols.

    Science.gov (United States)

    Vale, Vlad R; Will, Stefan; Schröer, Wolffram; Rathke, Bernd

    2012-05-14

    The liquid-liquid equilibrium (LLE) phase behavior of mixtures of 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide (C(2)mimNTf(2)) with the n-alkyl alcohols (C(n)OH; 3≤n≤8) is described. By applying the cloud-point method, the LLEs were determined over a temperature range of 275-423 K at ambient pressure. Partial miscibility with upper critical solution temperatures (UCST) was observed. The UCST increase with increasing chain length of the alcohols. The phase diagrams were analyzed numerically by presuming Ising criticality. Concepts for the description of the asymmetry of the phase diagram by presuming the validity of the rectilinear diameter rule or a nonlinear diameter requested by the theory of complete scaling were applied. The results (UCST, critical composition, width and diameter of the phase diagrams) are compared with similar systems and discussed in terms of the corresponding state behavior; they map on a single curve. From at least 45 individual phase diagrams, general aspects of the behavior of this ionic liquid-alcohol mixture type were extracted. A simple empirical relationship was formulated to allow the description of the UCST with an accuracy of about 10 K when taking the ratio of the molar volumes of the alcohol and the 1-alkyl-3-methylimidazolium cation of the ionic liquid into account. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 瞬间弹射蒸汽爆破增强离子液体对水稻秸秆的预处理效果%Enhanced effects of ionic liquid pretreatment on rice straw by instant catapult steam explosion

    Institute of Scientific and Technical Information of China (English)

    覃锦程; 郝学密; 刘黎阳; 刘晨光; 白凤武

    2015-01-01

    选取具有不同组分分离效果的离子液体 1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)和 1-乙基-3-甲基咪唑氯盐([Emim]Cl),并联用瞬间弹射蒸汽爆破(instant catapult steam explosion, ICSE)对水稻秸秆进行预处理.离子液体导致了组分的重排,使纤维素更多地暴露于物料表面,同时减弱了木质素对纤维素紧密交联的程度.ICSE的使用提升了离子液体的预处理效果,酶解糖收率比单纯使用离子液体升高了14.83%([Emim]Ac)和13.14%([Emim]Cl),其中ICSE联用[Emim]Ac的糖收率最高达97.00%.采用扫描电镜(SEM)和热重分析仪(TGA)进行物料结构分析,证实了ICSE联用离子液体有助于破坏物料的致密结构,增加无定形区,从而提高酶解糖收率.%In this study, two kinds of ionic liquid, including 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium chloride were used to pretreat rice straw with instant catapult steam explosion (ICSE). The rearrangement of components were caused by ionic liquid pretreatment, which made more cellulose exposed at the surface of rice straw and weakened the cross-link between lignin and cellulose. Through enzymatic hydrolysis analysis, ICSE enhanced the effects of ionic liquid pretreatment by improving the sugar yield. Compared with the sugar yield as using ionic liquid alone, the sugar yield as combination of ICSE and ionic liquid increased by 14.83% ([Emim]Ac) and 13.14% ([Emim]Cl). The highest value reached 97.00% under the pretreatment by ICSE combine with [Emim]Ac. The structural changes were also analyzed by scanning electron microscope (SEM) and thermo gravimetric analysis (TGA). The pretreated materials became more porous with larger amorphous region, and consequently the sugar yield raised.

  13. A Simple AIMD Approach to Derive Atomic Charges for Condensed Phase Simulation of Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Y; Maginn, EJ

    2012-08-23

    The atomic charges for two ionic liquids (ILs), 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM] [PF6]) and 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM][PF6]), were derived from periodic crystal phase calculations with density functional theory (DFT) and plane wave basis sets (denoted as "AIMD-c charge"). For both ILs, the total charge was found to be +/- 0.8 e for the cation and anion, respectively, due to the charge transfer between ions and polarization caused by the environment. These atomic charges were used in a force field developed within the general Amber force field framework. Using this force field, static, dynamic, and thermodynamic properties were computed for the two ILs using molecular dynamics simulation. The results were compared against results obtained using the same Amber force field but four different sets of partial charges, denoted as full charge, scaled charge, AIMD-1 charge, and AIMD-b charge, respectively. The full charge was derived from quantum chemistry calculation of isolated ions in a vacuum and resulted in a total charge of unity on each ion. The scaled charge was obtained by uniformly scaling the full charge by 0.8. AIMD-1 and AIMD-b charges were derived from liquid phase ab initio molecular dynamics simulations. The scaled charges have the same total charge on the ions as the AIMD-c charge but different distributions. It was found that simulation results not only depend on the total charge of each ion, but they are also sensitive to the charge distribution within an ion, especially for dynamic and thermodynamic properties. Overall, for the two ILs under study, the AIMD-c charge was found to predict experimental results better than the other four sets of charges, indicating that fitting charges from crystal phase DFT calculations, instead of extensive sampling of the liquid phase configurations, is a simple and reliable way to derive atomic charges for condensed phase ionic liquid simulations.

  14. A facile approach to prepare regenerated cellulose/graphene nanoplatelets nanocomposite using room-temperature ionic liquid.

    Science.gov (United States)

    Mahmoudian, Shaya; Wahit, Mat Uzir; Imran, Muhammad; Ismail, A F; Balakrishnan, Harintharavimal

    2012-07-01

    This study presents the preparation of regenerated cellulose (RC)/graphene nanoplatelets (GNPs) nanocomposites via room temperature ionic liquid, 1-ethyl-3-methylimidazolium acetate (EMIMAc) using solution casting method. The thermal stability, gas permeability, water absorption and mechanical properties of the films were studied. The synthesized nanocomposite films were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The T20 decomposition temperature of regenerated cellulose improved with the addition of graphene nanoplatelets up to 5 wt%. The tensile strength and Young's modulus of RC films improved by 34 and 56%, respectively with the addition of 3 wt% GNPs. The nanocomposite films exhibited improved oxygen and carbon dioxide gas barrier properties and water absorption resistance compared to RC. XRD and SEM results showed good interaction between RC and GNPs and well dispersion of graphene nanoplatelets in regenerated cellulose. The FTIR spectra showed that the addition of GNPs in RC did not result in any noticeable change in its chemical structure.

  15. Ion-cage interpretation for the structural and dynamic changes of ionic liquids under an external electric field.

    Science.gov (United States)

    Shi, Rui; Wang, Yanting

    2013-05-01

    In many applications, ionic liquids (ILs) work in a nonequilibrium steady state driven by an external electric field. However, how the electric field changes the structure and dynamics of ILs and its underlying mechanism still remain poorly understood. In this paper, coarse-grained molecular dynamics simulations were performed to investigate the structure and dynamics of 1-ethyl-3-methylimidazolium nitrate ([EMIm][NO3]) under a static electric field. The ion cage structure was found to play an essential role in determining the structural and dynamic properties of the IL system. With a weak or moderate electric field (0-10(7) V/m), the external electric field is too weak to modify the ion cage structure in an influential way and thus the changes of structural and dynamic properties are negligible. With a strong electric field (10(7)-10(9) V/m) applied, ion cages expand and deform apparently, leading to the increase of ion mobility and self-diffusion coefficient with electric field, and the self-diffusion of ions along the electric field becomes faster than the other two directions due to the anisotropic deformation of ion cages. In addition, the Einstein relation connecting diffusion and mobility breaks down at strong electric fields, and it also breaks down for a single ion species even at moderate electric fields (linear-response region).

  16. Characterization of the Micromorphology and Topochemistry of Poplar Wood during Mild Ionic Liquid Pretreatment for Improving Enzymatic Saccharification

    Directory of Open Access Journals (Sweden)

    Sheng Chen

    2017-01-01

    Full Text Available Ionic liquids (ILs as designer solvents have been applied in biomass pretreatment to increase cellulose accessibility and therefore improve the enzymatic hydrolysis. We investigated the characterization of the micromorphology and the topochemistry of poplar wood during 1-ethyl-3-methylimidazolium acetate pretreatment with mild conditions (90 °C for 20 and 40 min by multiple microscopic techniques (FE-SEM, CLSM, and CRM. Chemical composition analysis, XRD, cellulase adsorption isotherm, and enzymatic hydrolysis were also performed to monitor the variation of substrate properties. Our results indicated that the biomass conversion was greatly enhanced (from 20.57% to 73.64% due to the cell wall deconstruction and lignin dissolution (29.83% lignin was removed after incubation for 40 min, rather than the decrystallization or crystallinity transformation of substrates. The mild ILs pretreatment, with less energy input, can not only enhance enzymatic hydrolysis, but also provide a potential approach as the first step in improving the sequential pretreatment effectiveness in integrated methods. This study provides new insights on understanding the ILs pretreatment with low temperature and short duration, which is critical for developing individual and/or combined pretreatment technologies with reduced energy consumption.

  17. Engineering the electrochemical capacitive properties of graphene sheets in ionic-liquid electrolytes by correct selection of anions.

    Science.gov (United States)

    Shi, Minjie; Kou, Shengzhong; Yan, Xingbin

    2014-11-01

    Graphene sheet (GS)-ionic liquid (IL) supercapacitors are receiving intense interest because their specific energy density far exceeds that of GS-aqueous electrolytes supercapacitors. The electrochemical properties of ILs mainly depend on their diverse ions, especially anions. Therefore, identifying suitable IL electrolytes for GSs is currently one of the most important tasks. The electrochemical behavior of GSs in a series of ILs composed of 1-ethyl-3-methylimidazolium cation (EMIM(+)) with different anions is systematically studied. Combined with the formula derivation and building models, it is shown that the viscosity, ion size, and molecular weight of ILs affect the electrical conductivity of ILs, and thus, determine the electrochemical performances of GSs. Because the EMIM-dicyanamide IL has the lowest viscosity, ion size, and molecular weight, GSs in it exhibit the highest specific capacitance, smallest resistance, and best rate capability. In addition, because the tetrafluoroborate anion (BF4(-)) has the best electrochemical stability, the GS-[EMIM][BF4] supercapacitor has the widest potential window, and thus, displays the largest energy density. These results may provide valuable information for selecting appropriate ILs and designing high-performance GS-IL supercapacitors to meet different needs.

  18. Effect of ionic liquid pretreatment on the chemical composition, structure and enzymatic hydrolysis of energy cane bagasse.

    Science.gov (United States)

    Qiu, Zenghui; Aita, Giovanna M; Walker, Michelle S

    2012-08-01

    Ionic liquids (ILs) are promising solvents for the pretreatment of lignocellulose as they are thermally stable, environmentally friendly, recyclable, and have low volatility. This study evaluated the effect of 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) for the pretreatment of energy cane bagasse in terms of biomass composition, structural changes and enzymatic digestibility. Energy cane bagasse was pretreated with [EMIM][OAc] (5% (w/w)) at 120 °C for 30 min followed by hydrolysis with commercially available enzymes, Spezyme CP and Novozyme 188. IL-treated energy cane bagasse resulted in significant lignin removal (32.0%) with slight glucan and xylan losses (8.8% and 14.0%, respectively), and exhibited a much higher enzymatic digestibility (87.0% and 64.3%) than untreated (5.5% and 2.8%) or water-treated (4.0% and 2.1%) energy cane bagasse in terms of both cellulose and hemicellulose digestibilities, respectively. The enhanced digestibilities of IL-treated biomass can be attributed to delignification and reduction of cellulose crystallinity as confirmed by FTIR and XRD analyses.

  19. Self-assembly of azobenzene bilayer membranes in binary ionic liquid-water nanostructured media.

    Science.gov (United States)

    Kang, Tejwant Singh; Ishiba, Keita; Morikawa, Masa-aki; Kimizuka, Nobuo

    2014-03-11

    Anionic azobenzene-containing amphiphile 1 (sodium 4-[4-(N-methyl-N-dodecylamino)phenylazo]benzenesulfonate) forms ordered bilayer membranes in binary ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, [C2mim][C2OSO3])-water mixtures. The binary [C2mim][C2OSO3]-water mixture is macroscopically homogeneous at any mixing ratio; however, it possesses fluctuating nanodomains of [C2mim][C2OSO3] molecules as observed by dynamic light scattering (DLS). These nanodomains show reversible heat-induced mixing behavior with water. Although the amphiphile 1 is substantially insoluble in pure water, it is dispersible in the [C2mim][C2OSO3]-water mixtures. The concentration of [C2mim][C2OSO3] and temperature exert significant influences on the self-assembling characteristics of 1 in the binary media, as shown by DLS, transmission electron microscopy (TEM), UV-vis spectroscopy, and zeta-potential measurements. Bilayer membranes with rod- or dotlike nanostructures were formed at a lower content of [C2mim][C2OSO3] (2-30 v/v %), in which azobenzene chromophores adopt parallel molecular orientation regardless of temperature. In contrast, when the content of [C2mim][C2OSO3] is increased above 60 v/v %, azobenzene bilayers showed thermally reversible gel-to-liquid crystalline phase transition. The self-assembly of azobenzene amphiphiles is tunable depending on the volume fraction of [C2mim][C2OSO3] and temperature, which are associated with the solvation by nanoclusters in the binary [C2mim][C2OSO3]-water media. These observations clearly indicate that mixtures of water-soluble ionic liquids and water provide unique and valiant environments for ordered molecular self-assembly.

  20. An ionic liquid supported CeO2 nanoparticles-carbon nanotubes composite-enhanced electrochemical DNA-based sensor for the detection of Pb2+

    Institute of Scientific and Technical Information of China (English)

    Yan Lia; Xiao-Rong Liut; Xiao-Hui Ning; Can-Can Hnang; Jian-Bin Zheng; Jun-cai Zhang

    2011-01-01

    An electrochemical sensor incorporating a signal enhancement for the determination of lead (II) ions (Pb2+) was designed on the basis of the thrombin-binding aptamer (TBA) as a molecular recog- nition element and ionic liquid supported cerium oxide (CeO2) nanoparticles-carbon nanotubes compo- site modification. The composite comprises nanoparticles CeO2, multi-waU carbon nanotubes (MWNTs) and hydrophobic room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4). The electrochemical sensors were fabricated by immersing the CeOa-MWNTs-EMIMBF4 modified glassy carbon electrode (GCE) into the solution of TBA probe. In the presence of Pb2+, the TBA probe could form stable G-quartet structure by the specific binding interactions between Pb2+ and TBA. The TBA-bound Pb2+ can be electrochemically reduced, which provides a readout signal for quantitative detection of Pb2+. The reduction peak current is linearly related to the concentration of Pb2+ from 1.0 * 10-8 M to 1.0 * 105 M with a detection limit of 5 * 109 M. This work demonstrates that the CeOz-MWNTs-EMIMBF4 nanocomposite modified GCE provides a promising platform for immobi- lizing the TBA probe and enhancing the sensitivity of the DNA-based sensors.

  1. Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Jiao, Jiao; Ma, Dan-Hui; Gai, Qing-Yan; Wang, Wei; Luo, Meng; Fu, Yu-Jie; Ma, Wei

    2013-12-04

    A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C2mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 μL) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78°C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences.

  2. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry

    Energy Technology Data Exchange (ETDEWEB)

    Kruk, D. [Faculty of Mathematics and Computer Science, University of Warmia and Mazury in Olsztyn, Słoneczna 54, PL-10710 Olsztyn (Poland); Universität Bayreuth, Experimentalphysik II, 95440 Bayreuth (Germany); Meier, R.; Rössler, E. A. [Universität Bayreuth, Experimentalphysik II, 95440 Bayreuth (Germany); Rachocki, A. [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17, 60-179 Poznań (Poland); Korpała, A. [Department of Biophysics, Jagiellonian University Medical College, Łazarza 16, 31-530 Kraków, Poland and Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków (Poland); Singh, R. K. [Ionic Liquid and Solid State Ionics Laboratory, Department of Physics, Banaras Hindu University, Varanasi 221 005 (India)

    2014-06-28

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220–258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF{sub 4}, 243–318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF{sub 6}, 258–323 K). The dispersion of {sup 1}H spin-lattice relaxation rate R{sub 1}(ω) is measured in the frequency range of 10 kHz–20 MHz, and the studies are complemented by {sup 19}F spin-lattice relaxation measurements on BMIM-PF{sub 6} in the corresponding frequency range. From the {sup 1}H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF{sub 4}, and BMIM-PF{sub 6} are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the {sup 1}H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R{sub 1} on square root of frequency. From the {sup 19}F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF{sub 6}. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  3. One-pot integrated biofuel production using low-cost biocompatible protic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Jian; Konda, Murthy; Parthasarathi, Ramakrishnan; Dutta, Tanmoy; Valiev, Marat; Xu, Feng; Simmons, Blake A.; Singh, Seema

    2017-01-01

    The transformation of biomass into liquid fuels is of great importance. Previous work has demonstrated the capability of specific ionic liquids (ILs), such as 1-ethyl-3-methylimidazolium acetate ([C(2)C(1)Im][OAc]) and cholinium lysinate ([Ch][Lys]), to be effective biomass pretreatment solvents. Using these ILs for an integrated biomass-to-biofuel configuration is still challenging due to a significant water-wash related to the high toxicity of [C(2)C(1)Im][OAc] and pH adjustment prior to saccharification for the highly basic [Ch][Lys]. In this work, we demonstrate, for the first time, that a one-pot integrated biofuel production is enabled by a low cost (similar to$1 per kg) and biocompatible protic IL (PIL), ethanolamine acetate, without pH adjustments, water-wash and solid-liquid separations. After pretreatment, the whole slurry is directly used for simultaneous saccharification and fermentation (SSF) with commercial enzyme cocktails and wild type yeast strains, generating 70% of the theoretical ethanol yield (based on switchgrass). The structure-performance relationships of PILs in terms of lignin removal, net basicity, and pH value are systematically studied. A technoeconomic analysis (TEA) revealed that an integrated biorefinery concept based on this PIL process could potentially reduce the minimum ethanol selling price by more than 40% compared to scenarios that require pH adjustment prior to SSF. Improvement of the economic performance will be made by reducing the dilution and enzyme loading during SSF as identified by TEA. This study demonstrates the impact of a biocompatible IL in terms of process optimization and conversion efficiency, and opens up avenues for realizing an IL based efficiently integrated biomass conversion technology.

  4. Electrochemical and spectroscopic study of Zn(ii) coordination and Zn electrodeposition in three ionic liquids with the trifluoromethylsulfonate anion, different imidazolium ions and their mixtures with water.

    Science.gov (United States)

    Liu, Zhen; El Abedin, Sherif Zein; Endres, Frank

    2015-06-28

    In this paper we report on the use of three ionic liquids, 1-methylimidazolium trifluoromethylsulfonate ([MIm]TfO), 1-ethyl-3-methylimidazolium trifluoromethylsulfonate ([EMIm]TfO) and 1-ethyl-2,3-dimethylimidazolium trifluoromethylsulfonate ([EMMIm]TfO) containing zinc trifluoromethylsulfonate as electrolytes for zinc electrodeposition. By varying the cations from [MIm](+)via [EMIm](+) to [EMMIm](+), the vibrational band in the Far-IR spectra below 200 cm(-1), characterizing the cation-anion interaction, is shifted to lower wavenumbers, which suggests that the interaction between cations and anions is arranged in order of [MIm]TfO > [EMIm]TfO > [EMMIm]TfO. The coordination of Zn(2+) ions in these electrolytes was investigated by Raman spectroscopy. The Raman spectra show obvious differences in terms of the solvation of Zn(2+) ions in the dried electrolytes. The average number of TfO(-) anions bound to each Zn(2+) ion is lower in [MIm]TfO than in [EMIm]TfO and in [EMMIm]TfO, respectively. In ionic liquid-water mixtures, aqueous zinc species were formed in all cases. The differences in zinc species present in the electrolytes should have an influence on their electrochemical behavior and on the morphology of the deposits. In dried ionic liquids, the cyclic voltammograms reveal that the potentials for the deposition of zinc were shifted to more negative values by varying the cations, while in ionic liquid-water mixtures, the deposition of zinc occurs at almost the same potential. The SEM and XRD results show that the surface morphology, crystal shape and size as well as crystallographic orientation of the deposits are markedly affected by varying the cations of the ionic liquids.

  5. Polarity and Nonpolarity of Ionic Liquids Viewed from the Rotational Dynamics of Carbon Monoxide.

    Science.gov (United States)

    Yasaka, Y; Kimura, Y

    2015-12-17

    The rotational dynamics of carbon monoxide (CO) in a molten salt, ionic liquids (ILs), and alkanes were investigated by (17)O NMR T1 measurements using labeled C(17)O. The molten salt and the studied ILs have the bis(trifluoromethanesulfonyl)imide anion ([NTf2](-)) in common. In hexane near room temperature, the rotational relaxation times are close to the values predicted from the slip boundary condition in the Stokes-Einstein-Debye (SED) theory. However, in contradiction to the theoretical prediction, the rotational relaxation times decrease as the value of η/T increases, where η and T are the viscosity and absolute temperature, respectively. In other alkanes and ILs used in this study, the rotational relaxation times are much faster than those predicted by SED, and show a unique dependence on the number of alkyl carbons. For the same value of η/T, the CO rotational relaxation times in ILs composed of short-alkyl-chain-length imidazolium cations (1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium) are close to those for a molten salt (Cs[NTf2]). On the other hand, the rotational relaxation times in ILs composed of long-chain-length imidazolium (1-methyl-3-octylimidazolium) and phosphonium (tributylmethylphosphonium and tetraoctylphosphonium) cations are much shorter than the SED predictions. This deviation from theory increases as the alkyl chain length increases. We also found that the rotational relaxation times in dodecane and squalane are similar to those in ILs with a similar number of alkyl carbons. These results are discussed in terms of heterogeneous solvation and in comparison with the translational diffusion of CO in ILs.

  6. Molal Enthalpy of Solution of Ionic Liquid [C2mim][GaCl4

    Institute of Scientific and Technical Information of China (English)

    GUAN,Wei; LIU,Li; WANG,Caixia; YANG,Jiazhen

    2009-01-01

    An ionic liquid (IL),[C2mim][GaCl4](l-ethyl-3-methylimidazolium chlorogallate),was prepared by directly mixing 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and anhydrous GaCI3 with a molar ratio of 1/1 under dry argon.The molal enthalpies of solution,△sHm,of [C2mim][GaCl4],were measured over a molality range of about 0.008-0.1 mol·kg 1 by a solution reaction isoperibol calorimeter at 298.15 K.Considering the hydrolization of anion [GaCl4]- in dissolution process of the IL,a new method of determining the standard molal enthalpy of solution,△sH(⊙)m,was put forward on the basis of Pitzer's mixed electrolyte solution theory so that △sH(⊙)m = -132kJ·mol-1 and the sum of Pitzer's parameters;4β(0)GaCl + 4β(0)[C2mim].Cl + ΦGa,[C2mim]= -0.1373076,β(1)LGa,Cl + β(1)L[C2mim].C=0.3484209 were obtained.In terms of thermodynamic cycle and Glasser's theory of lattice energy for IL,the dissociation enthalpy of [GaCl4]-(g),△Hdis([GaCl4]-)≈5855 kJ·mol-1,that is enthalpy change for the reaction:[GaCl4]-(g)→Ga3+(g) +4Cl- (g),was estimated.

  7. Development of a carbohydrate silylation method in ionic liquids for their gas chromatographic analysis.

    Science.gov (United States)

    Ruiz-Aceituno, L; Carrero-Carralero, C; Ramos, L; Martinez-Castro, I; Sanz, M L

    2013-07-17

    This paper reports on the feasibility of silylation of low molecular weight carbohydrates dissolved in different ionic liquids (ILs) for their further analysis by gas chromatography (GC). Derivatization reagents (nature and amounts), temperature and time of reaction and stirring conditions were evaluated for different carbohydrates (i.e., glucose, mannose, fructose and lactose) dissolved in 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA]. Evaluation of conformational isomerism of glucose dissolved in [EMIM][DCA] revealed the effect of the time of dissolution in the equilibration of α- and β-furanoses (up to 3% and 6%, respectively, after 70 h of incubation) and that 21 h sufficed to obtain results similar to those provided by the reference method involving pyridine. Once optimized, the proposed derivatization procedure provided satisfactory yields (i.e., close to 100%) using 100 μL of trimethylsilylimidazole (TMSI) at mild conditions (25°C) for a relatively short time (1h) for most of the investigated carbohydrates. Under these experimental conditions, linear responses (i.e., R(2) better than 0.974) were obtained in the tested range of 0.25-1mg of the derivatized target compounds. Other reagents, such as N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS), were successfully used under ultrasonic conditions for aldose monosaccharides and disaccharides derivatization, while BSTFA was useful for ketose monosaccharides. The possibility of using the proposed method for the derivatization of selected carbohydrates dissolved in different ILs and the efficiency of the method applied to the analysis of carbohydrates present in real samples (fruit juices) have also been investigated.

  8. Graphene-based supercapacitors in the parallel-plate electrode configuration: ionic liquids versus organic electrolytes.

    Science.gov (United States)

    Shim, Youngseon; Kim, Hyung J; Jung, Younjoon

    2012-01-01

    Supercapacitors with two single-sheet graphene electrodes in the parallel plate geometry are studied via molecular dynamics (MD) computer simulations. Pure 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI+BF4-) and a 1.1 M solution of EMI+BF4- in acetonitrile are considered as prototypes of room-temperature ionic liquids (RTILs) and organic electrolytes. Electrolyte structure, charge density and associated electric potential are investigated by varying the charges and separation of the two electrodes. Multiple charge layers formed in the electrolytes in the vicinity of the electrodes are found to screen the electrode surface charge almost completely. As a result, the supercapacitors show nearly an ideal electric double layer behavior, i.e., the electric potential exhibits essentially a plateau behavior in the entire electrolyte region except for sharp changes in screening zones very close to the electrodes. Due to its small size and large charge separation, BF4- is considerably more efficient in shielding electrode charges than EMI+. In the case of the acetonitrile solution, acetonitrile also plays an important role by aligning its dipoles near the electrodes; however, the overall screening mainly arises from ions. Because of the disparity of shielding efficiency between cations and anions, the capacitance of the positively-charged anode is significantly larger than that of the negatively-charged cathode. Therefore, the total cell capacitance in the parallel plate configuration is primarily governed by the cathode. Ion conductivity obtained via the Green-Kubo (GK) method is found to be largely independent of the electrode surface charge. Interestingly, EMI+BF4- shows higher GK ion conductivity than the 1.1 M acetonitrile solution between two parallel plate electrodes.

  9. Quaternary ammonium room-temperature ionic liquid including an oxygen atom in side chain/lithium salt binary electrolytes: ab initio molecular orbital calculations of interactions between ions.

    Science.gov (United States)

    Tsuzuki, Seiji; Hayamizu, Kikuko; Seki, Shiro; Ohno, Yasutaka; Kobayashi, Yo; Miyashiro, Hajime

    2008-08-14

    Interactions of the lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) complex with N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium (DEME), 1-ethyl-3-methylimidazolium (EMIM) cations, neutral diethylether (DEE), and the DEMETFSA complex were studied by ab initio molecular orbital calculations. An interaction energy potential calculated for the DEME cation with the LiTFSA complex has a minimum when the Li atom has contact with the oxygen atom of DEME cation, while potentials for the EMIM cation with the LiTFSA complex are always repulsive. The MP2/6-311G**//HF/6-311G** level interaction energy calculated for the DEME cation with the LiTFSA complex was -18.4 kcal/mol. The interaction energy for the neutral DEE with the LiTFSA complex was larger (-21.1 kcal/mol). The interaction energy for the DEMETFSA complex with LiTFSA complex is greater (-23.2 kcal/mol). The electrostatic and induction interactions are the major source of the attraction in the two systems. The substantial attraction between the DEME cation and the LiTFSA complex suggests that the interaction between the Li cation and the oxygen atom of DEME cation plays important roles in determining the mobility of the Li cation in DEME-based room temperature ionic liquids.

  10. Synthesis and Characterisation of ETS-10/Acetate-based Ionic Liquid/Chitosan Mixed Matrix Membranes for CO2/N2 Permeation

    Directory of Open Access Journals (Sweden)

    Clara Casado-Coterillo

    2014-06-01

    Full Text Available Mixed matrix membranes (MMMs were prepared by incorporating organic surfactant-free hydrothermally synthesised ETS-10 and 1-ethyl-3-methylimidazolium acetate ionic liquid (IL to chitosan (CS polymer matrix. The membrane material characteristics and permselectivity performance of the two-component membranes were compared with the three-component membrane and the pure CS membrane. The addition of IL increased CO2 solubility of the polymer, and, thus, the CO2 affinity was maintained for the MMMs, which can be correlated with the crystallinity, measured by FT-IR, and void fraction calculations from differences between theoretical and experimental densities. The mechanical resistance was enhanced by the ETS-10 nanoparticles, and flexibility decreased in the two-component ETS-10/CS MMMs, but the flexibility imparted by the IL remained in three-component ETS-10/IL/CS MMMs. The results of this work provide insight into another way of facing the adhesion challenge in MMMs and obtain CO2 selective MMMs from renewable or green chemistry materials.

  11. Synthesis and Characterisation of ETS-10/Acetate-based Ionic Liquid/Chitosan Mixed Matrix Membranes for CO2/N2 Permeation.

    Science.gov (United States)

    Casado-Coterillo, Clara; Del Mar López-Guerrero, María; Irabien, Angel

    2014-06-19

    Mixed matrix membranes (MMMs) were prepared by incorporating organic surfactant-free hydrothermally synthesised ETS-10 and 1-ethyl-3-methylimidazolium acetate ionic liquid (IL) to chitosan (CS) polymer matrix. The membrane material characteristics and permselectivity performance of the two-component membranes were compared with the three-component membrane and the pure CS membrane. The addition of IL increased CO2 solubility of the polymer, and, thus, the CO2 affinity was maintained for the MMMs, which can be correlated with the crystallinity, measured by FT-IR, and void fraction calculations from differences between theoretical and experimental densities. The mechanical resistance was enhanced by the ETS-10 nanoparticles, and flexibility decreased in the two-component ETS-10/CS MMMs, but the flexibility imparted by the IL remained in three-component ETS-10/IL/CS MMMs. The results of this work provide insight into another way of facing the adhesion challenge in MMMs and obtain CO2 selective MMMs from renewable or green chemistry materials.

  12. Sensors for Highly Toxic Gases: Methylamine and Hydrogen Chloride Detection at Low Concentrations in an Ionic Liquid on Pt Screen Printed Electrodes

    Science.gov (United States)

    Murugappan, Krishnan; Silvester, Debbie S.

    2015-01-01

    Commercially available Pt screen printed electrodes (SPEs) have been employed as possible electrode materials for methylamine (MA) and hydrogen chloride (HCl) gas detection. The room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) was used as a solvent and the electrochemical behaviour of both gases was first examined using cyclic voltammetry. The reaction mechanism appears to be the same on Pt SPEs as on Pt microelectrodes. Furthermore, the analytical utility was studied to understand the behaviour of these highly toxic gases at low concentrations on SPEs, with calibration graphs obtained from 10 to 80 ppm. Three different electrochemical techniques were employed: linear sweep voltammetry (LSV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV), with no significant differences in the limits of detection (LODs) between the techniques (LODs were between 1.4 to 3.6 ppm for all three techniques for both gases). The LODs achieved on Pt SPEs were lower than the current Occupational Safety and Health Administration Permissible Exposure Limit (OSHA PEL) limits of the two gases (5 ppm for HCl and 10 ppm for MA), suggesting that Pt SPEs can successfully be combined with RTILs to be used as cheap alternatives for amperometric gas sensing in applications where these toxic gases may be released. PMID:26506358

  13. Sensors for Highly Toxic Gases: Methylamine and Hydrogen Chloride Detection at Low Concentrations in an Ionic Liquid on Pt Screen Printed Electrodes

    Directory of Open Access Journals (Sweden)

    Krishnan Murugappan

    2015-10-01

    Full Text Available Commercially available Pt screen printed electrodes (SPEs have been employed as possible electrode materials for methylamine (MA and hydrogen chloride (HCl gas detection. The room temperature ionic liquid (RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([C2mim][NTf2] was used as a solvent and the electrochemical behaviour of both gases was first examined using cyclic voltammetry. The reaction mechanism appears to be the same on Pt SPEs as on Pt microelectrodes. Furthermore, the analytical utility was studied to understand the behaviour of these highly toxic gases at low concentrations on SPEs, with calibration graphs obtained from 10 to 80 ppm. Three different electrochemical techniques were employed: linear sweep voltammetry (LSV, differential pulse voltammetry (DPV and square wave voltammetry (SWV, with no significant differences in the limits of detection (LODs between the techniques (LODs were between 1.4 to 3.6 ppm for all three techniques for both gases. The LODs achieved on Pt SPEs were lower than the current Occupational Safety and Health Administration Permissible Exposure Limit (OSHA PEL limits of the two gases (5 ppm for HCl and 10 ppm for MA, suggesting that Pt SPEs can successfully be combined with RTILs to be used as cheap alternatives for amperometric gas sensing in applications where these toxic gases may be released.

  14. Enhanced Photocatalytic Reduction of CO2 to CO through TiO2 Passivation of InP in Ionic Liquids.

    Science.gov (United States)

    Zeng, Guangtong; Qiu, Jing; Hou, Bingya; Shi, Haotian; Lin, Yongjing; Hettick, Mark; Javey, Ali; Cronin, Stephen B

    2015-09-21

    A robust and reliable method for improving the photocatalytic performance of InP, which is one of the best known materials for solar photoconversion (i.e., solar cells). In this article, we report substantial improvements (up to 18×) in the photocatalytic yields for CO2 reduction to CO through the surface passivation of InP with TiO2 deposited by atomic layer deposition (ALD). Here, the main mechanisms of enhancement are the introduction of catalytically active sites and the formation of a pn-junction. Photoelectrochemical reactions were carried out in a nonaqueous solution consisting of ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF4), dissolved in acetonitrile, which enables CO2 reduction with a Faradaic efficiency of 99% at an underpotential of +0.78 V. While the photocatalytic yield increases with the addition of the TiO2 layer, a corresponding drop in the photoluminescence intensity indicates the presence of catalytically active sites, which cause an increase in the electron-hole pair recombination rate. NMR spectra show that the [EMIM](+) ions in solution form an intermediate complex with CO2(-), thus lowering the energy barrier of this reaction.

  15. Determination of phase transition points of ionic liquids by combination of thermal analysis and conductivity measurements at very low heating and cooling rates

    Energy Technology Data Exchange (ETDEWEB)

    Wachter, Philipp; Schreiner, Christian; Schweiger, Hans-Georg [Workgroup Electrochemistry and Electrolytes, Institute of Physical and Theoretical Chemistry, University of Regensburg, Universitaetsstr. 31, D-93040 Regensburg (Germany); Gores, Heiner Jakob, E-mail: Heiner.Gores@Chemie.Uni-Regensburg.d [Workgroup Electrochemistry and Electrolytes, Institute of Physical and Theoretical Chemistry, University of Regensburg, Universitaetsstr. 31, D-93040 Regensburg (Germany)

    2010-07-15

    The determination of phase transition points of nine different ionic liquids (ILs) was performed by thermal analysis with simultaneous recording of conductivity. Conductivity of electrolyte solutions and ILs drastically changes during phase transitions and thus is an additional and very sensitive indicator for measuring phase transition points. Evaluation of temperature-time functions and conductivity-time functions with our computer-coupled automated equipment enabled the determination of melting temperatures with high accuracy and reliability. This claim is based on large samples, low temperature change rates and by regularly repeated measurements, i.e. at least seven measurements per IL. The melting temperatures of 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium tris(penta-fluoroethyl)trifluorophosphate, and 1-methyl-3-propylimidazolium iodide were, to our knowledge, determined for the first time. The melting temperatures of the other 1-butyl-1-methylpyrrolidinium-, 1-ethyl-3-methylimidazolium-, 1-hexyl-3-methylimidazolium-, and trimethylsulfonium-based ILs showed either a very good accordance with values published in literature or were distinctly higher.

  16. A Comparison of the Effects of Prenatal Exposure of CD-1 Mice to Three Imidazolium-Based Ionic Liquids

    Science.gov (United States)

    Bailey, Melissa M.; Jernigan, Peter L.; Henson, Megan B.; Sturdivant, John; Rasco, Jane F.; Lovich, Ashley N.; Lockhard, Jarrett E.; Hough, Whitney; Di Bona, Kristin R.; Beaird, Janis; Sherrill, Jonathan; Swatloski, Richard P.; Rogers, Robin D.; Hood, Ronald D.

    2015-01-01

    BACKGROUND Ionic liquids (ILs; salts with melting points below 100 °C) exhibit wide liquid ranges, non-flammability, and thermal stability among other properties. These unique salts are best known as ‘green’ alternatives to traditional volatile organic solvents, which are utilized in both academia and industry. Our current study compares the developmental toxicity potential of three representative ionic liquids, with various chain lengths: 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl), 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), and 1-decyl-3methylimidazolium chloride ([C10mim]Cl). METHODS From gestation days (GD) 6-16, mated CD-1 mice were orally dosed with one of the following: 1000, 2000, or 3000 mg/kg/day [C2mim]Cl; 113, 169, or 225 mg/kg/day [C4mim]Cl; 50, 75, or 100 mg/kg/day [C10mim]Cl; or the vehicle only. Dams were sacrificed on GD 17, and their litters were examined for adverse effects. RESULTS Fetal weight was significantly decreased in the two highest dosage groups exposed to [C4mim]Cl and [C10mim]Cl in comparison with their controls, but the [C2mim]Cl treated groups were not affected. An apparent teratogenic effect was associated with both [C4mim]Cl and [C10mim]Cl, as the offspring exhibited certain uncommon morphological defects. However, the incidences of malformations were low and no correlation between incidence and dosage could be made. No morphological defects were observed in any of the [C2mim]Cl-treated groups, despite maternal morbidity at the highest dosage level. CONCLUSIONS This study indicates that [C4mim]Cl and [C10mim]Cl may have adverse effects on development at high maternal exposures and strongly supports the supposition that the toxicity of imidazolium-based ILs is influenced by alkyl chain length. PMID:20540104

  17. Atomistic Simulation and Electronic Structure of Lithium Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability

    Science.gov (United States)

    Haskins, Justin B.; Bauschlicher, Charles W.; Lawson, John W.

    2015-01-01

    Zero-temperature density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Lithium ion on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N--methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N--methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3--methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Lithium ion solvation shell through zero-temperature DFT simulations of [Li(Anion)sub n](exp n-1) -clusters, DFT-MD simulations of isolated lithium ions in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having 2-3 anions are seen in both [pyr14][TFSI] and [pyr13][FSI], while solvation shells with 4 anions dominate in [EMIM][BF sub 4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of 4 anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion) sub n](exp n -1) - clusters shows that our proposed structures are consistent with experiment. We estimate the ion diffusion coefficients and quantify both size and simulation time effects. We find estimates of lithium ion diffusion are a reasonable order of magnitude and can be corrected for simulation time effects. Simulation size, on the other hand, is also important, with diffusion coefficients from long PFF-MD simulations of small cells having 20-40% error compared to large-cell values. Finally, we compute the electrochemical window using differences in electronic energy levels of both isolated cation/anion pairs and small ionic liquid systems with Li-salt doping. The single pair and liquid

  18. Determination and modelling of osmotic coefficients and vapour pressures of binary systems 1- and 2-propanol with C{sub n}MimNTf{sub 2} ionic liquids (n = 2, 3, and 4) at T = 323.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Calvar, Noelia [LSRE - Laboratory of Separation and Reaction Engineering, Associate Laboratory, LSRE/LCM, Department of Chemical Engineering, Faculty of Engineering, Rua Dr. Roberto Frias s/n, Porto 4200-465 (Portugal); Gomez, Elena; Dominguez, Angeles [Advanced Separation Processes Group, Department of Chemical Engineering, University of Vigo, 36310 Vigo (Spain); Macedo, Eugenia A., E-mail: eamacedo@fe.up.pt [LSRE - Laboratory of Separation and Reaction Engineering, Associate Laboratory, LSRE/LCM, Department of Chemical Engineering, Faculty of Engineering, Rua Dr. Roberto Frias s/n, Porto 4200-465 (Portugal)

    2011-08-15

    Highlights: > Osmotic coefficients of 1- and 2-propanol with C{sub n}MimNTf{sub 2} (n = 2, 3, and 4) are determined. > Experimental data were correlated with extended Pitzer model of Archer and MNRTL. > Mean molal activity coefficients and excess Gibbs free energies were calculated. > Effect of the anion is studied comparing these results with literature. - Abstract: The osmotic and activity coefficients and vapour pressures of binary mixtures containing 1-propanol, or 2-propanol and imidazolium-based ionic liquids with bis(trifluoromethylsulfonyl)imide as anion (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, C{sub 2}MimNTf{sub 2}, 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, C{sub 3}MimNTf{sub 2}, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, C{sub 4}MimNTf{sub 2}) were determined at T = 323.15 K using the vapour pressure osmometry technique. The experimental osmotic coefficients were correlated using the extended Pitzer model modified by Archer and the MNRTL model, obtaining standard deviations lower than 0.033 and 0.064, respectively. The mean molal activity coefficients and the excess Gibbs free energy for the mixtures studied were calculated from the parameters of the extended Pitzer model modified by Archer. Besides the effect of the alkyl-chain of the cation, the effect of the anion can be assessed comparing the experimental results with those previously obtained for imidazolium ionic liquids with sulphate anions.

  19. Unusual phase separation and rheological behavior of poly(ethylene oxide)/ionic liquid mixtures with specific interactions.

    Science.gov (United States)

    Xiao, Zhilin; Larson, Ronald G; Chen, Yunlei; Zhou, Chenting; Niu, Yanhua; Li, Guangxian

    2016-09-28

    The phase separation behavior of poly(ethylene oxide) (PEO) in ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) was investigated by rheological, optical microscopy, FT-IR and DSC measurements. It is demonstrated that specific interactions, particularly the hydrogen bonding between PEO and the ionic liquids as evidenced by FT-IR, in which a subtle but apparent absorption peak shift near the phase transition appears, account for the unusual low critical solution temperature (LCST) phase separation. Unlike the typical trend in which the storage modulus G' simply increases with temperature near the phase boundary for polymer blends without specific interaction, in our study, a novel "V-shaped" rheological response is observed, namely a dip in G' followed by an upturn, especially at low PEO concentration (<50 wt%). The magnitude of the "V" dip has heating rate and frequency dependences, while Tr (the phase transition temperature) is almost unchanged with heating rate and frequency. Upon increasing the alkyl chain length on the imidazolium ring from an ethyl to a butyl, the "V-shape" becomes more prominent and shifts to higher temperature, which is consistent with the results of FT-IR and DSC, evidently due to the stronger hydrogen bonding interaction between PEO and [BMIM][BF4] than [EMIM][BF4]. This unusual "V" dip might be tentatively ascribed to the coupling effects of the breaking of the "hydrogen bonding cage" formed between PEO chains and IL molecules and dissolution of the heterogeneous clusters as verified by FT-IR and TEM, respectively, and the following upturn is dominated by the interface formation upon phase separation.

  20. Ionic-liquid-based ultrasound-assisted extraction of isoflavones from Belamcanda chinensis and subsequent screening and isolation of potential α-glucosidase inhibitors by ultrafiltration and semipreparative high-performance liquid chromatography.

    Science.gov (United States)

    Li, Senlin; Li, Sainan; Huang, Yu; Liu, Chunming; Chen, Lina; Zhang, Yuchi

    2017-06-01

    The separation of a compound of interest from its structurally similar homologues to produce high-purity natural products is a challenging problem. This work proposes a novel method for the separation of iristectorigenin A from its structurally similar homologues by ionic-liquid-based ultrasound-assisted extraction and the subsequent screening and isolation of potential α-glucosidase inhibitors via ultrafiltration and semipreparative high-performance liquid chromatography. Ionic-liquid-based ultrasound-assisted extraction was successfully applied to the extraction of tectorigenin, iristectorigenin A, irigenin, and irisflorentin from Belamcanda chinensis. The optimum conditions for the efficient extraction of isoflavones were determined as 1.0 M 1-ethyl-3-methylimidazolium tetrafluoroborate with extraction time of 30 min and a solvent to solid ratio of 30 mL/g. Ultrafiltration with liquid chromatography and mass spectrometry was applied to screen and identify α-glucosidase inhibitors from B. chinensis, followed by the application of semipreparative high-performance liquid chromatography to separate and isolate the active constituents. Four major compounds including tectorigenin, iristectorigenin A, irigenin, and irisflorentin were screened and identified as α-glucosidase inhibitors, and then the four active compounds abovementioned were subsequently isolated by semipreparative high-performance liquid chromatography (99.89, 88.97, 99.79, and 99.97% purity, respectively). The results demonstrate that ionic liquid extraction can be successfully applied to the extraction of isoflavones from B. chinensis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Inelastic and Reactive Scattering Dynamics of Hyperthermal Oxygen Atoms on Ionic Liquid Surfaces: [emim][NTf2] and [C12mim][NTf2

    Science.gov (United States)

    Wu, Bohan; Zhang, Jianming; Minton, Timothy K.; McKendrick, Kenneth G.; Slattery, John M.; Yockel, Scott; Schatz, George C.

    2011-05-01

    Collisions of hyperthermal oxygen atoms, with an average translational energy of 520 kJ mol-1, on continuously refreshed ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][NTf2]) and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C12mim][NTf2]), were studied with the use of a beam-surface scattering technique. Time-of-flight and angular distributions of inelastically scattered O and reactively scattered OH and H2O were collected for various angles of incidence with the use of a rotatable mass spectrometer detector. For both O and OH, two distinct scattering processes were identified, which can be empirically categorized as thermal and non-thermal. Non-thermal scattering is more probable for both O and OH products. The observation of OH confirms that at least some reactive sites, presumably alkyl groups, must be exposed at the surface. The ionic liquid with the longer alkyl chain, [C12mim][NTf2], is substantially more reactive than the liquid with the shorter alkyl chain, [emim][NTf2], and proportionately much more so than would be predicted simply from stoichiometry based on the number of abstractable hydrogen atoms. Molecular dynamics models of these surfaces shed light on this change in reactivity. The scattering behavior of O is distinctly different from that of OH. However, no such differences between inelastic and reactive scattering dynamics have been seen in previous work on pure hydrocarbon liquids, in particular the benchmark, partially branched hydrocarbon, squalane (C30H62). The comparison between inelastic and reactive scattering dynamics indicates that inelastic scattering from the ionic liquid surfaces takes place predominantly at non-reactive sites that are effectively stiffer than the reactive alkyl chains, with a higher proportion of collisions sampling such sites for [emim][NTf2] than for [C12mim][NTf2].

  2. Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid%Rapid conversion of cellulose to5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

    Institute of Scientific and Technical Information of China (English)

    Hussein Abou-Yousef; El Barbary Hassan; Philip Steele

    2013-01-01

    Direct conversion of cellulose into 5-hydroxymethylfurfural (HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride ([EMIM] Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone (FHMK),and furfural (FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives (HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF (35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeC13/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF (39.9%) with total yield (63.8%) of fttrans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals (5 ~ 20 min).

  3. Dynamics of methanol in ionic liquids: validity of the Stokes-Einstein and Stokes-Einstein-Debye relations.

    Science.gov (United States)

    Herold, Elisabeth; Strauch, Matthias; Michalik, Dirk; Appelhagen, Andreas; Ludwig, Ralf

    2014-10-06

    The validity of Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations for methanol in the physical environment of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is studied by means of nuclear magnetic resonance (NMR) relaxation time experiments, viscosity measurements and molecular dynamics (MD) simulations. The reorientational correlation times of the hydroxyl groups of pure methanol and of methanol in the IL/methanol mixtures were determined. For that purpose an approach for estimating NMR deuteron quadrupole coupling constants, presented by Wendt and Farrar (Mol. Phys. 1998, 95, 1077-1081), was confirmed. The self-diffusion coefficients of methanol were taken from the MD simulations. The viscosities of all systems were then measured and the SE and SED relations validated. For pure methanol both relations are valid, whereas they become increasingly invalid with increasing IL concentration, as indicated by effective volumes and radii that are too low. The deviation from the SE and SED relations could be related to dynamical heterogeneities described by the non-Gaussian parameter α(t) obtained from MD simulations. For pure methanol, α(t) is close to zero in accord with the validity of both relations. With increasing IL concentration the dynamical heterogeneities of methanol increase strongly. The times t* at the maximum of α(t) increase linearly with the relative number of methanol monomers in the mixtures. Thus, the dynamical heterogeneities are largest for single methanol molecules fully embedded in the IL environment. In their own environment methanol molecules are highly mobile, whereas in the IL-rich region the mobility is strongly reduced leading to the non-validity of SE and SED relations.

  4. Study of surface interactions of ionic liquids with aluminium alloys in corrosion and erosion-corrosion processes

    Energy Technology Data Exchange (ETDEWEB)

    Bermudez, Maria-Dolores [Grupo de Ciencia de Materiales e Ingenieria Metalurgica, Departamento de Ingenieria de Materiales y Fabricacion, Universidad Politecnica de Cartagena, C/ Doctor Fleming s/n, Campus Muralla del Mar, 30202 Cartagena (Spain)]. E-mail: mdolores.bermudez@upct.es; Jimenez, Ana-Eva [Grupo de Ciencia de Materiales e Ingenieria Metalurgica, Departamento de Ingenieria de Materiales y Fabricacion, Universidad Politecnica de Cartagena, C/ Doctor Fleming s/n, Campus Muralla del Mar, 30202 Cartagena (Spain); Martinez-Nicolas, Gines [Grupo de Ciencia de Materiales e Ingenieria Metalurgica, Departamento de Ingenieria de Materiales y Fabricacion, Universidad Politecnica de Cartagena, C/ Doctor Fleming s/n, Campus Muralla del Mar, 30202 Cartagena (Spain)

    2007-06-30

    Surface interactions of alkylimidazolium ionic liquids (ILs) with aluminium alloy Al 2011 have been studied by immersion tests in seven neat ILs [1-n-alkyl-3-methylimidazolium X{sup -} (X = BF{sub 4}; n = 2 (IL1), 6 (IL2), 8 (IL3). X = CF{sub 3}SO{sub 3}; n = 2 (IL4). X = (4-CH{sub 3}C{sub 6}H{sub 4}SO{sub 3}); n = 2 (IL5). X PF{sub 6}; n = 6 (IL6)] and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (IL7)]. Immersion tests for Al 2011 have also been carried out in 1 wt.% and 5 wt.% solutions of 1-ethyl,3-methylimidazolium tetrafluoroborate (IL1) in water. No corrosion of Al 2011 by neat ILs is observed. The highest corrosion rate for Al 2011 in water is observed in the presence of a 5 wt.% IL1 due to hydrolysis of the anion with hydrogen evolution and formation of aluminium fluoride. Erosion-corrosion processes have been studied for three aluminium alloys (Al 2011, Al 6061 and Al 7075) in a 90 wt.% IL1 solution in water in the presence of {alpha}-alumina particles. The erosion-corrosion rates are around 0.2 mm/year or lower, and increase with increasing copper content to give a corrosion resistance order of Al 6061 > Al 7075 > Al 2011. Results are discussed on the basis of scanning electron microscopy (SEM) observations, energy dispersive spectroscopy (EDS) analysis, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) determinations.

  5. Surface coating from phosphonate ionic liquid electrolyte for the enhancement of the tribological performance of magnesium alloy.

    Science.gov (United States)

    Jiménez, Ana Eva; Rossi, Antonella; Fantauzzi, Marzia; Espinosa, Tulia; Arias-Pardilla, Joaquin; Martínez-Nicolás, Ginés; Bermúdez, María-Dolores

    2015-05-20

    A chronoamperometric method has been applied for the growth of a surface coating on AZ31B magnesium alloy, using the imidazolium alkylphosphonate room-temperature ionic liquid 1-ethyl-3-methylimidazolium ethylphosphonate ([EMIM][EtPO3H]) as electrolyte. A surface coating layer is obtained after 4 h under a constant voltage bias of -0.8 V with respect to the standard electrode. The coating nucleation and growth process correlates well with a 3D progressive mechanism. X-ray photoelectron spectrometry (XPS) analysis of [EMIM][EtPO3H] shows new P 2p and O 1s peaks after its use as electrolyte, as a consequence of reaction between the phosphonate anion and the magnesium substrate. Angle-resolved XPS (ARXPS) analysis of [EMIM][EtPO3H] did not show any change in the composition of the surface before and after chronoamperometry, since the sampling depth (1.5 nm at the highest emission angle) is larger than the cation and anion sizes (ca. 7 and 5 Å, respectively). Characterization of the coating was made by scanning electron microscopy (SEM), focussed ion beam SEM, energy dispersive X-ray spectroscopy, XPS, and ARXPS. FIB-SEM shows that the coating presents a mean thickness of 374 (±36) nm and contains magnesium and aluminum phosphates. Linear reciprocating tribological tests under variable load show that the presence of the coating can reduce friction coefficients of the coated AZ31B against steel up to 32% and wear rates up to 90%, with respect to the uncoated alloy.

  6. Effects of water concentration on the structural and diffusion properties of imidazolium-based ionic liquid-water mixtures.

    Science.gov (United States)

    Niazi, Amir A; Rabideau, Brooks D; Ismail, Ahmed E

    2013-02-07

    We have used molecular dynamics simulations to study the properties of three ionic liquid (IL)-water systems: 1-butyl-3-methylimidazolium chloride ([bmim]Cl), 1-ethyl-3-methylimidazolium acetate ([emim][Ac]), and 1,3-dimethylimidazolium dimethylphosphate ([dmim][DMP]). We observe the transition of those mixtures from pure IL to aqueous solution by analyzing the changes in important bulk properties (density) and structural and bonding properties (radial distribution functions, water clustering, hydrogen bonding, and cationic stacking) as well as dynamical properties (diffusion coefficients) at 12 different concentration samplings of each mixture, ranging from 0.0 to 99.95 mol % water. Our simulations revealed across all of the different structural, bonding, and dynamical properties major structural changes consistent with a transition from IL-water mixture to aqueous solution in all three ILs at water concentrations around 75 mol %. Among the structural changes observed were rapid increase in the frequency of hydrogen bonds, both water-water and water-anion. Similarly, at these critical concentrations, the water clusters formed begin to span the entire simulation box, rather than existing as isolated networks of molecules. At the same time, there is a sudden decrease in cationic stacking at the transition point, followed by a rapid increase near 90 mol % water. Finally, the diffusion coefficients of individual cations and anions show a rapid transition from rates consistent with diffusion in IL's to rates consistent with diffusion in water beginning at 75 mol % water. The location of this transition is consistent, for [bmim]Cl and [dmim][DMP], with the water concentration limit above which the ILs are unable to dissolve cellulose.

  7. Acidic Ionic Liquids.

    Science.gov (United States)

    Amarasekara, Ananda S

    2016-05-25

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

  8. 玉米秸秆在两种咪唑类离子液体中的溶解与再生%Cornstalk dissolution and regeneration in two imidazolium-based ionic liquids

    Institute of Scientific and Technical Information of China (English)

    李姗; 李增喜; 朱敏莉; 吕兴梅

    2013-01-01

    研究1-丁基-3-甲基咪唑氯盐(BmimCl)和1-乙基-3-甲基咪唑乙酸盐(EmimOAc)两种咪唑类离子液体在不同条件下对玉米秸秆的溶解和再生情况.采用傅里叶变换红外光谱(IR)、X-射线粉末衍射(XRD)、扫描电镜(SEM)热重分析(TGA)手段分析溶解前后秸秆的化学结构与结晶结构.结果表明,秸秆纤维素溶解再生后结晶度变低,热稳定性也略有降低;离子液体是秸秆的直接溶剂,秸秆在其中并未发生衍生化反应.%Dissolution of cornstalk in l-butyl-3-methylimidazolium chloride (BmimCl) and 1-ethyl-3-methylimidazolium acetate (EmimOAc) was studied. Chemical structure and crystalline form of cornstalk before and after dissolution were analyzed by means of FT-IR, TGA, SEM , and XRD. The results show that the crystallinity and thermostability of the regenerated cellulose-rich material slightly decreased after dissolution. Cornstalk directly dissolved in ionic liquids, and no derivatization reaction occurred.

  9. A Disposable Amperometric Sensor Based on High-Performance PEDOT:PSS/Ionic Liquid Nanocomposite Thin Film-Modified Screen-Printed Electrode for the Analysis of Catechol in Natural Water Samples

    Directory of Open Access Journals (Sweden)

    Francis D. Krampa

    2017-07-01

    Full Text Available A conducting polymer-based composite material of poly(3,4-ethylenedioxythiophene (PEDOT: poly(4-styrenesulfonate (PSS doped with different percentages of a room temperature ionic liquid (IL, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4], was prepared and a very small amount of the composite (2.0 µL was drop-coated on the working area of a screen-printed carbon electrode (SPCE. The SPCE, modified with PEDOT:PSS/IL composite thin-film, was characterized by cyclic voltammetry (CV, electrochemical impedance spectroscopy (EIS, scanning electron microscopy (SEM, profilometry and sessile contact angle measurements. The prepared PEDOT:PSS/IL composite thin-film exhibited a nano-porous microstructure and was found to be highly stable and conductive with enhanced electrocatalytic properties towards catechol, a priority pollutant. The linear working range for catechol was found to be 0.1 µM–330.0 µM with a sensitivity of 18.2 mA·mM·cm−2 and a calculated limit of detection (based on 3× the baseline noise of 23.7 µM. When the PEDOT:PSS/IL/SPCE sensor was used in conjunction with amperometry in stirred solution for the analysis of natural water samples, the precision values obtained on spiked samples (20.0 µM catechol added (n = 3 were 0.18% and 0.32%, respectively, with recovery values that were well over 99.0%.

  10. Molecular dynamics analysis of the effect of electronic polarization on the structure and single-particle dynamics of mixtures of ionic liquids and lithium salts.

    Science.gov (United States)

    Lesch, Volker; Montes-Campos, Hadrián; Méndez-Morales, Trinidad; Gallego, Luis Javier; Heuer, Andreas; Schröder, Christian; Varela, Luis M

    2016-11-28

    We report a molecular dynamics study on the effect of electronic polarization on the structure and single-particle dynamics of mixtures of the aprotic ionic liquid 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide ([EMIM][TFSI]) doped with a lithium salt with the same anion at 298 K and 1 bar. In particular, we analyze the effect of electron density fluctuations on radial distribution functions, velocity autocorrelation functions, cage correlation functions, mean-squared displacements, and vibrational densities of states, comparing the predictions of the quantum-chemistry-based Atomistic Polarizable Potential for Liquids, Electrolytes, & Polymers (APPLE&P) with those of its nonpolarizable version and those of the standard non-polarizable Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA). We found that the structure of the mixture is scarcely modified by the fluctuations in electron charge of their constituents, but their transport properties are indeed quite drastically changed, with larger mobilities being predicted for the different species in the bulk mixtures with the polarizable force field. Specifically, the mean-squared displacements are larger for the polarizable potentials at identical time intervals and the intermediate subdiffusive plateaus are greatly reduced, so the transition to the diffusive regime takes place much earlier than in the non-polarizable media. Moreover, the correlations of the added cations inside their cages are weakened out earlier and their vibrational densities of states are slightly red-shifted, reflecting the weakening effect of the electronic polarization on the Coulomb coupling in these dense ionic media. The comparison of OPLS-AA with non-polarizable APPLE&P indicates that adding polarization to OPLS-AA is not sufficient to achieve results close to experiments.

  11. Molecular dynamics analysis of the effect of electronic polarization on the structure and single-particle dynamics of mixtures of ionic liquids and lithium salts

    Science.gov (United States)

    Lesch, Volker; Montes-Campos, Hadrián; Méndez-Morales, Trinidad; Gallego, Luis Javier; Heuer, Andreas; Schröder, Christian; Varela, Luis M.

    2016-11-01

    We report a molecular dynamics study on the effect of electronic polarization on the structure and single-particle dynamics of mixtures of the aprotic ionic liquid 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide ([EMIM][TFSI]) doped with a lithium salt with the same anion at 298 K and 1 bar. In particular, we analyze the effect of electron density fluctuations on radial distribution functions, velocity autocorrelation functions, cage correlation functions, mean-squared displacements, and vibrational densities of states, comparing the predictions of the quantum-chemistry-based Atomistic Polarizable Potential for Liquids, Electrolytes, & Polymers (APPLE&P) with those of its nonpolarizable version and those of the standard non-polarizable Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA). We found that the structure of the mixture is scarcely modified by the fluctuations in electron charge of their constituents, but their transport properties are indeed quite drastically changed, with larger mobilities being predicted for the different species in the bulk mixtures with the polarizable force field. Specifically, the mean-squared displacements are larger for the polarizable potentials at identical time intervals and the intermediate subdiffusive plateaus are greatly reduced, so the transition to the diffusive regime takes place much earlier than in the non-polarizable media. Moreover, the correlations of the added cations inside their cages are weakened out earlier and their vibrational densities of states are slightly red-shifted, reflecting the weakening effect of the electronic polarization on the Coulomb coupling in these dense ionic media. The comparison of OPLS-AA with non-polarizable APPLE&P indicates that adding polarization to OPLS-AA is not sufficient to achieve results close to experiments.

  12. Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography–mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jiao, Jiao [State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040 (China); Ma, Dan-Hui [College of Life Sciences, Northeast Forestry University, Harbin 150040 (China); Gai, Qing-Yan; Wang, Wei; Luo, Meng [State Engineering Laboratory of Bio-Resource Eco-Utilization, Northeast Forestry University, Harbin 150040 (China); Fu, Yu-Jie, E-mail: yujie_fu2002@yahoo.com [State Engineering Laboratory of Bio-Resource Eco-Utilization, Northeast Forestry University, Harbin 150040 (China); Ma, Wei, E-mail: mawei@hljucm.net [State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040 (China); School of Pharmaceutical, Heilongjiang University of Chinese Medicine, Harbin 150040 (China)

    2013-12-04

    Graphical abstract: -- Highlights: •A new ILAMD-HS-SDME method is developed for the microextraction of essential oil. •ILs used as destruction agent of plant cell walls and microwave absorption medium. •Parameters affecting the extraction efficiency are optimized by Box–Behnken design. •Procedure benefits: similar constituents, shorter duration and smaller sample amount. •ILAMD-HS-SDME followed by GC–MS is a promising technique in analytical fields. -- Abstract: A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C{sub 2}mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 μL) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78 °C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences.

  13. Using ionic liquid as the solvent to prepare Pd–Ni bimetallic nanoparticles by a pyrolysis method for ethanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Keqiang, E-mail: dkeqiang@263.net [College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024 (China); Yang, Hongwei; Cao, Yanli; Zheng, Chunbao [College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024 (China); Rapole, Sowjanya B. [Integrated Composites Laboratory (ICL), Dan F. Smith Department of Chemical Engineering, Lamar University, Beaumont, TX 77710 (United States); Guo, Zhanhu, E-mail: zhanhu.guo@lamar.edu [Integrated Composites Laboratory (ICL), Dan F. Smith Department of Chemical Engineering, Lamar University, Beaumont, TX 77710 (United States)

    2013-10-01

    Room temperature ionic liquids (RTILs) of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) is used as the solvent for the first time to prepare multi-walled carbon nanotubes (MWCNTs) supported nanocomposite catalysts of Pd{sub x}Ni{sub y} (atomic ratios of Pd to Ni are 1:1, 1:1.5, 1:2, and 1:2.5) nanoparticles (denoted as Pd{sub x}Ni{sub y}/MWCNTs) by using a simple pyrolysis process. The Pd{sub x}Ni{sub y}/MWCNTs catalysts are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results show that the Pd{sub x}Ni{sub y} nanoparticles (NPs) are quite uniformly dispersed on the surface of MWCNTs with an average crystallite size of ∼7.0 nm. The electro-catalytic activity of the Pd{sub x}Ni{sub y}/MWCNTs catalysts for ethanol oxidation reaction (EOR) is examined by cyclic voltammetry (CV). It is revealed that the onset potential is ∼80 mV lower and the peak current is about three times higher for ethanol oxidation for MWCNT catalysts with Pd{sub 1}Ni{sub 1.5} compared to those of Pd/MWCNTs. The catalytic mechanisms of the Pd{sub 1}Ni{sub 1.5}/MWCNTs towards EOR are also proposed and discussed. - Highlights: • Introducing ionic liquids to the pyrolysis process for the preparation of Pd{sub x}Ni{sub y} nanoparticles. • Pd{sub x}Ni{sub y} nanoparticles with an average particle size of ∼7.0 nm were fabricated. • The peak current of EOR was about three times higher at Pd{sub 1}Ni{sub 1.5} compared to those of Pd.

  14. SO(2) saturation of the room temperature ionic liquid [C(2)mim][NTf(2)] much reduces the activation energy for diffusion.

    Science.gov (United States)

    Barrosse-Antle, Laura E; Hardacre, Christopher; Compton, Richard G

    2009-01-29

    The physical effect of high concentrations of reversibly dissolved SO(2) on [C(2)mim][NTf(2)] was examined using cyclic voltammetry, chronoamperometry, and ESR spectroscopy. Cyclic voltammetry of the oxidation of solutions of ferrocene, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), and chloride in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethanesufonyl)imide ([C(2)mim][NTf(2)]) reveals an increase in limiting current of each species corresponding to the addition of increasing concentrations of sulfur dioxide. Quantitative chronoamperometry reveals an increase in each species' diffusion coefficient with SO(2) concentration. When chronoamperometric data were obtained for ferrocene in [C(2)mim][NTf(2)] at a range of temperatures, the translational diffusion activation energy (29.0 +/- 0.5 kJ mol(- 1)) was found to be in good agreement with previous studies. Adding SO(2) results in apparent near-activationless translational diffusion. A significant decrease in the activation energy of rotational diffusion with the SO(2) saturation of a 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) solution in [C(2)mim][NTf(2)] (29.9 +/- 2.0 to 7.7 +/- 5.3 kJ mol(- 1)) was observed using electron spin resonance (ESR) spectroscopy. The reversible physical absorption of SO(2) by [C(2)mim][NTf(2)] should have no adverse effect on the ability of that ionic liquid to be employed as a solvent in an electrochemical gas sensor, and it is possible that the SO(2)-mediated reduction of RTIL viscosity could have intrinsic utility.

  15. Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

    Science.gov (United States)

    Leadbetter, Kirt C.

    . Advancements of this nonaqueous aluminum plating process have the potential to lead to a novel and competitive commercial aluminum deposition process. In this investigation aluminum electrodeposition from ionic liquid based electrolytes onto steel, copper and magnesium substrates without conversion coatings or strike layers was evaluated in six different ionic liquid based electrolytes in two technical setups. Three of which are commercially available aluminum plating electrolytes, three of which, discussed in literature were created on site by research personnel in the laboratory. The three commercially available electrolytes were: 1-Butyl-3-methylimidazolium chloride ([BMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, 1-Ethyl-3-methylimidazolium chloride ([EMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, and BasionicsTM AL-02, an aluminum plating electrolyte containing [EMIm]Cl * 1.5 AlCl3 with additives from BASF. The three electrolytes created on site were based on the 1-ethyl-3-methylimidazolium chloride ionic liquid with added 1.5 AlCl3 and one with added sodium dodecyl sulfate. Small scale plating tests in a 25-mL plating cell were conducted to provide a comparative analysis of the six different electrolytes considered. From these investigations, two were chosen to be evaluated in a larger 1-liter plating cell; designed and constructed to provide a more realistic evaluation of plating parameters with selected electrolytes to better portray industrial electroplating conditions. The effect of current density (10-40 mA/cm 2), temperature (30-90° Celsius) and plating bath agitation on current efficiency, corrosion resistance by the ASTM B117 method, adhesion, microstructure, and chemical composition (evaluated with energy-dispersive x-ray spectroscopy) of the plated Al-layer was explored in both the 25-mL and 1-L plating cell investigations. In addition development of pre- and post-treatment processes for the metal substrates was attempted. While

  16. Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

    Science.gov (United States)

    Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

    2014-01-01

    We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of

  17. Modeling of ionic liquids

    Science.gov (United States)

    Tatlipinar, Hasan

    2017-02-01

    Ionic liquids are very important entry to industry and technology. Because of their unique properties they may classified as a new class of materials. IL usually classified as a high temperature ionic liquids (HTIL) and room temperature ionic liquids (RTIL). HTIL are molten salts. There are many research studies on molten salts such as recycling, new energy sources, rare elements mining. RTIL recently become very important in daily life industry because of their "green chemistry" properties. As a simple view ionic liquids consist of one positively charged and one negatively charged components. Because of their Coulombic or dispersive interactions the local structure of ionic liquids emerges. In this presentation the local structural properties of the HTIL are discussed via correlation functions and integral equation theories. RTIL are much more difficult to do modeling, but still general consideration for the modeling of the HTIL is valid also for the RTIL.

  18. Cellulose hydrolysis and binding with Trichoderma reesei Cel5A and Cel7A and their core domains in ionic liquid solutions.

    Science.gov (United States)

    Wahlström, Ronny; Rahikainen, Jenni; Kruus, Kristiina; Suurnäkki, Anna

    2014-04-01

    Ionic liquids (ILs) dissolve lignocellulosic biomass and have a high potential as pretreatment prior to total enzymatic hydrolysis. ILs are, however, known to inactivate cellulases. In this article, enzymatic hydrolysis of microcrystalline cellulose (MCC) and enzyme binding onto the cellulosic substrate were studied in the presence of cellulose-dissolving ILs. Two different ILs, 1,3-dimethylimidazolium dimethylphosphate ([DMIM]DMP) and 1-ethyl-3-methylimidazolium acetate ([EMIM]AcO), and two monocomponent cellulases, Trichoderma reesei cellobiohydrolase Cel7A and endoglucanase Cel5A, were used in the study. The role and IL sensitivity of the carbohydrate-binding module (CBM) were studied by performing hydrolysis and binding experiments with both the intact cellulases, and their respective core domains (CDs). Based on hydrolysis yields and substrate binding experiments for the intact enzymes and their CDs in the presence of ILs, the function of the CBM appeared to be very IL sensitive. Binding data suggested that the CBM was more important for the substrate binding of endoglucanase Cel5A than for the binding of cellobiohydrolase Cel7A. The CD of Cel7A was able to bind well to cellulose even without a CBM, whereas Cel5A CD had very low binding affinity. Hydrolysis also occurred with Cel5A CD even if this protein had very low binding affinity in all the studied matrices. Binding and hydrolysis were less affected by the studied ILs for Cel7A than for Cel5A. To our knowledge, this is the first systematic study of IL effects on cellulase substrate binding. © 2013 Wiley Periodicals, Inc.

  19. Effect of the structure of imidazolium cations in [BF4](-)-type ionic liquids on direct electrochemistry and electrocatalysis of horseradish peroxidase in Nafion films.

    Science.gov (United States)

    Lu, Lu; Huang, Xirong; Qu, Yinbo

    2011-10-01

    The direct electrochemistry and bioelectrocatalysis of horseradish peroxidase (HRP) in Nafion films at glassy carbon electrode (GCE) was investigated in three [BF(4)](-)-type room-temperature ionic liquids (ILs) to understand the structural effect of imidazolium cations. The three ILs are 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF(4)]), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) and 1-hexyl-3-methylimidazolium tetrafluoroborate ([Hmim][BF(4)]). A small amount of water in the three ILs is indispensable for maintaining the electrochemical activity of HRP in Nafion films, and the optimum water contents decrease with the increase of alkyl chain length on imidazole ring. Analysis shows that the optimum water contents are primarily determined by the hydrophilicity of ILs used. In contrast to aqueous medium, ILs media facilitate the direct electron transfer of HRP, and the electrochemical parameters obtained in different ILs are obviously related to the nature of ILs. The direct electron transfer between HRP and GCE is a surface-confined quasi-reversible single electron transfer process. The apparent heterogeneous electron transfer rate constant decreases gradually with the increase of alkyl chain length on imidazole ring, but the changing extent is relatively small. The electrocatalytic reduction current of H(2)O(2) at the present electrode decreases obviously with the increase of alkyl chain length, and the mass transfer of H(2)O(2) via diffusion in ILs should be responsible for the change. In addition, the modified electrode has good stability and reproducibility; the ability to tolerate high levels of F(-) has been greatly enhanced due to the use of Nafion film. When an appropriate mediator is included in the sensing layer, a sensitive nonaqueous biosensor could be fabricated. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Electrochemical characterisations and ageing of ionic liquid/γ-butyrolactone mixtures as electrolytes for supercapacitor applications over a wide temperature range

    Science.gov (United States)

    Dagousset, Laure; Pognon, Grégory; Nguyen, Giao T. M.; Vidal, Frédéric; Jus, Sébastien; Aubert, Pierre-Henri

    2017-08-01

    Electrochemical properties in mesoporous media of three different ionic liquids (1-propyl-1-methylpyrrolidinium-bis(fluorosulfonyl)imide - Pyr13FSI, 1-butyl-1-methylpyrrolidinium-bis(trifluoromethanesulfonyl)imide - Pyr14TFSI and 1-ethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide - EMITFSI) are investigated from -50 °C to 100 °C and compared with binary mixtures with γ-butyrolactone (GBL). Buckypaper composed of Single-Wall Carbon Nanotubes (SWCNTs) are used to prepare and study coin-cell supercapacitors. Supercapacitor using Pyr13FSI/GBL present a rapid loss of capacitance after only a thousand cycles at 100 °C. On the contrary, EMITFSI/GBL and Pyr14TFSI/GBL prove to be very promising at high temperature (the capacitance loss after 10,000 cycles is 9% and 10%). More drastic ageing tests such as floating are also carried out for these two mixtures at 100 °C and -50 °C. 23% and 15% capacitance losses have been recorded after 500 h of floating at 100 °C for EMITFSI/GBL and Pyr14TFSI/GBL. The capacitance of supercapacitors based on Pyr14TFSI/GBL dropped by 20% after 200 h of floating at -50 °C rather than EMITFSI/GBL show a remarkable stability during floating at -50 °C, with 6.6% capacitance loss after 500 h (3 V at -50 °C). These results show that the mixture EMITFSI/GBL works properly all along the broad range of temperature [-50 °C to +100 °C] and thus proved that our approach is very promising for the development of high performances supercapacitors specifically adapted for extreme environment.

  1. 基于离子液体的聚丙烯腈/纤维素共混体系溶解与流变性能研究%Research on dissolution and rheological properties of polyacrylonitrile/cellulose solution based on ionic liquids

    Institute of Scientific and Technical Information of China (English)

    张瑞民; 李晓俊; 程春祖; 尹翠玉

    2012-01-01

    采用旋转流变仪对以1-乙基-3-甲基咪唑醋酸盐([EMIM]Ac)为溶剂的聚丙烯腈/纤维素溶液的流变性能进行了研究.结果表明,溶液表观黏度随浓度的升高而增大,但随剪切速率的增加而降低,为典型的切力变稀流体;单组分PAN溶液A黏度最低,单组分纤维素溶液F黏度最大,不同共混比溶液的黏度及对温度的依赖性均介于两纯组分PAN和纤维素Cell之间.%The ionic liquid of 1-ethyl-3-methylimidazolium chloride ( [ EMIM ] Ac ) was used to dissolve polyacrlonitrile/cellulose, and then its rheological properties was studied with rotational rheometer. The results showed that: [ EMIM ] Ac was the good solvent both for cellulose and polyacrlonitrile. Solutions presented typical shear thinner fluid, the apparent shear viscosity decreased with the increase in shear rate, and increased with the increase in solutions' concentration. Single component PAN solution A had the lowest viscosity, while, the pure cellulose solution F had the highest, and viscosity of different blend ratio and the dependency to temperature both between pure solution PAN and cellulose.

  2. 咪唑类离子液体在纤维素酶降解纤维素体系中的作用%Function of imidazolium-based ionic liquids in system of enzymatic degradation of cellulose

    Institute of Scientific and Technical Information of China (English)

    范琳; 王少君; 李坤兰

    2015-01-01

    Taking 1-ethyl-3-methylimidazolium diethyl phosphate ([Emim]DEP) and 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) as research targets, the influence of the two ionic liquids (IL) on the process of enzymatic degradation of cellulose was investigated. By using ultrasound to assist ionic liquids in dissolving cellulose, [Emim]DEP and [Emim]Ac made the crystallinity of cellulose decrease to 53.6%and 62.3%respectively. In the process of enzymatic degradation of regenerated cellulose, when the dosage of IL was less than 2.0%, IL acted as promoter, and when the dosage of IL was 0.5%, the promoting effect of IL was the strongest. Enzymatic hydrolysis rate increased by 11.4% and 17.5% respectively. Under the optimal conditions (add in 0.5% IL), the enzyme activities of every enzyme in the cellulose system were measured. Ionic liquids had an obvious promoting effect on β-glucosidase, increasing enzyme activity by 120% and 87% respectively. Ionic liquids reduced inhibition of exoglucanase by cellubiose, and improved efficiency of enzymatic degradation of cellulose.%以1-乙基-3-甲基咪唑磷酸二乙酯([Emim]DEP)、1-乙基-3-甲基咪唑醋酸([Emim]Ac)为研究对象,考察两种离子液体(IL)对酶法降解纤维素过程的影响。采用超声辅助离子液体溶解纤维素,[Emim]DEP和[Emim]Ac分别使纤维素的结晶度降为53.6%和62.3%。在纤维素酶降解再生纤维素的过程中,当IL的加入量小于2.0%时,对酶解过程起促进作用,其中加入量为0.5%时,促进作用最强,酶解率分别提高了11.4%和17.5%。在最优条件下(加入0.5%IL),测量纤维素酶系中各个酶的酶活,结果表明离子液体对β-葡萄糖苷酶起到了明显的促进作用,分别使该酶酶活提高了120%和87%。离子液体降低了纤维二糖对葡聚糖外切酶的抑制作用,提高了酶解效率。

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

    Energy Technology Data Exchange (ETDEWEB)

    Lucas, Marcel [Los Alamos National Laboratory; Macdonald, Brian A [Los Alamos National Laboratory; Wagner, Gregory L [Los Alamos National Laboratory; Joyce, Steven A [Los Alamos National Laboratory; Rector, Kirk D [Los Alamos National Laboratory

    2010-01-01

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

  4. Activation of lignocellulosic biomass for higher sugar yields using aqueous ionic liquid at low severity process conditions.

    Science.gov (United States)

    Parthasarathi, Ramakrishnan; Sun, Jian; Dutta, Tanmoy; Sun, Ning; Pattathil, Sivakumar; Murthy Konda, N V S N; Peralta, Angelo Gabriel; Simmons, Blake A; Singh, Seema

    2016-01-01

    Concerns around greenhouse gas emissions necessitate the development of sustainable processes for the production of chemicals, materials, and fuels from alternative renewable sources. The lignocellulosic plant cell walls are one of the most abundant sources of carbon for renewable bioenergy production. Certain ionic liquids (ILs) are very effective at disrupting the plant cell walls of lignocellulose, and generate a substrate that is effectively hydrolyzed into fermentable sugars. Conventional ILs are relatively expensive in terms of purchase price, and the most effective imidazolium-based ILs also require energy intensive processing conditions (>140 °C, 3 h) to release >90 % fermentable sugar yields after saccharification. We have developed a highly effective pretreatment technology utilizing the relatively inexpensive IL comprised tetrabutylammonium [TBA](+) and hydroxide [OH](-) ions that generate high glucose yields (~95 %) after pretreatment at very mild processing conditions (50 °C). The efficiency of [TBA][OH] pretreatment of lignocellulose was further studied by analyzing chemical composition, powder X-ray diffraction for cellulose structure, NMR and SEC for lignin dissolution/depolymerization, and glycome profiling for cell wall modifications. Glycome profiling experiments and computational results indicate that removal of the noncellulosic polysaccharides occurs due to the ionic mobility of [TBA][OH] and is the key factor in determining pretreatment efficiency. Process modeling and energy demand analysis suggests that this [TBA][OH] pretreatment could potentially reduce the energy required in the pretreatment unit operation by more than 75 %. By leveraging the benefits of ILs that are effective at very mild processing conditions, such as [TBA][OH], lignocellulosic biomass can be pretreated at similar efficiency as top performing conventional ILs, such as 1-ethyl-3-methylimidazolium acetate [C2C1Im][OAc], but at much lower temperatures, and with

  5. Ionic liquids in tribology.

    Science.gov (United States)

    Minami, Ichiro

    2009-06-24

    Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

  6. Ionic Liquids in Tribology

    Directory of Open Access Journals (Sweden)

    Ichiro Minami

    2009-06-01

    Full Text Available Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

  7. Poly(ethylene oxide)-Based Composite Electrolytes Filled with Periodic Mesoporous Silica for Solid State Ionics

    Science.gov (United States)

    Tominaga, Yoichi; Morita, Masahiro; Asai, Shigeo; Sumita, Masao

    Mesoporous silica (MPS) was used for poly(ethylene oxide) (PEO)-based solid polymer electrolytes as novel inorganic filler. For improvement in ionic conductivity in solid state, a room temperature ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate, was introduced into periodic nano-tunnels of MPS, and the modified MPS (IL-MPS) was filled with PEO-LiBF4 electrolyte. Ionic conductivity of neat-MPS-filled composites was approximately 4-fold higher than that of the original electrolyte. On the other hand, the conductivity was more than 11-fold enhanced by addition of IL-MPS, to be more than 10-6 S/cm at 30°C and at least 10 wt% silica contents. The conductivity increased with increasing IL-MPS contents, to be a maximum value of approximately 3×10-6 S/cm at 30°C and at 40 wt%. Dynamic mechanical measurements for neat- and IL-MPS composites revealed that the addition of fillers improves storage modulus of PEO-based electrolytes at room temperature. The addition of IL-MPS was able to realize the improvement in both ionic conductivity and storage modulus.

  8. Organic transistors making use of room temperature ionic liquids as gating medium

    Science.gov (United States)

    Hoyos, Jonathan Javier Sayago

    The ability to couple ionic and electronic transport in organic transistors, based on pi conjugated organic materials for the transistor channel, can be particularly interesting to achieve low voltage transistor operation, i.e. below 1 V. The operation voltage in typical organic transistors based on conventional dielectrics (200 nm thick SiO2) is commonly higher than 10 V. Electrolyte-gated (EG) transistors, i.e. employing an electrolyte as the gating medium, permit current modulations of several orders of magnitude at relatively low gate voltages thanks to the exceptionally high capacitance at the electrolyte/transistor channel interface, in turn due to the low thickness (ca. 3 nm) of the electrical double layers forming at the electrolyte/semiconductor interface. Electrolytes based on room temperature ionic liquids (RTILs) are promising in EG transistor applications for their high electrochemical stability and good ionic conductivity. The main motivation behind this work is to achieve low voltage operation in organic transistors by making use of RTILs as gating medium. First we demonstrate the importance of the gate electrode material in the EG transistor performance. The use of high surface area carbon gate electrodes limits undesirable electrochemical processes and renders unnecessary the presence of a reference electrode to monitor the channel potential. This was demonstrated using activated carbon as gate electrode, the electronic conducting polymer MEH-PPV, poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] channel material, and the ionic liquid [EMIM][TFSI] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), as gating medium. Using high surface area gate electrodes resulted in sub-1 V operation and charge carrier mobilities of (1.0 +/- 0.5) x 10-2 cm2V -1s-1. A challenge in the field of EG transistors is to decrease their response time, a consequence of the slow ion redistribution in the transistor channel upon application of electric

  9. Ionic liquids in chemical engineering.

    Science.gov (United States)

    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.

  10. Comparison of the local binding motifs in the imidazolium-based ionic liquids [EMIM][BF4] and [EMMIM][BF4] through cryogenic ion vibrational predissociation spectroscopy: Unraveling the roles of anharmonicity and intermolecular interactions

    Science.gov (United States)

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; McCoy, Anne B.; Johnson, Mark A.

    2015-02-01

    We clarify the role of the critical imidazolium C(2)H position (the central C between N atoms in the heterocycle) in the assembly motif of the [EMIM][BF4] ionic liquid by analyzing the vibrational spectra of the bare EMIM+ ion as well as that of the cationic [EMIM]2[BF4]+ (EMIM+ = 1-ethyl-3-methylimidazolium, C6H11N2+) cluster. Vibrational spectra of the cold, mass-selected ions are obtained using cryogenic ion vibrational predissociation of weakly bound D2 molecules formed in a 10 K ion trap. The C(2)H behavior is isolated by following the evolution of key vibrational features when the C(2) hydrogen, the proposed binding location of the anion to the imidazolium ring, is replaced by either deuterium or a methyl group (i.e., in the EMMIM+ analogue). Strong features in the ring CH stretching region of the bare ion are traced to Fermi resonances with overtones of lower frequency modes. Upon incorporation into the EMIM+ ṡ ṡ ṡ BF4- ṡ ṡ ṡ EMIM+ ternary complex, the C(2)H oscillator strength is dramatically increased, accounting for the much more complicated patterns derived from the EMIM+ ring CH stretches in the light isotopomer, which are strongly suppressed in the deuterated analogue. Further changes in the spectra that occur when the C(2)H is replaced by a methyl group are consistent with BF4- attachment directly to the imidazolium ring in an arrangement that maximizes the electrostatic interaction between the molecular ions.

  11. Comparison of the local binding motifs in the imidazolium-based ionic liquids [EMIM][BF{sub 4}] and [EMMIM][BF{sub 4}] through cryogenic ion vibrational predissociation spectroscopy: Unraveling the roles of anharmonicity and intermolecular interactions

    Energy Technology Data Exchange (ETDEWEB)

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; Johnson, Mark A., E-mail: mark.johnson@yale.edu, E-mail: mccoy@chemistry.ohio-state.edu [Sterling Chemistry Laboratory, Yale University, New Haven, Connecticut 06520 (United States); McCoy, Anne B., E-mail: mark.johnson@yale.edu, E-mail: mccoy@chemistry.ohio-state.edu [Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210 (United States)

    2015-02-14

    We clarify the role of the critical imidazolium C{sub (2)}H position (the central C between N atoms in the heterocycle) in the assembly motif of the [EMIM][BF{sub 4}] ionic liquid by analyzing the vibrational spectra of the bare EMIM{sup +} ion as well as that of the cationic [EMIM]{sub 2}[BF{sub 4}]{sup +} (EMIM{sup +} = 1-ethyl-3-methylimidazolium, C{sub 6}H{sub 11}N{sub 2}{sup +}) cluster. Vibrational spectra of the cold, mass-selected ions are obtained using cryogenic ion vibrational predissociation of weakly bound D{sub 2} molecules formed in a 10 K ion trap. The C{sub (2)}H behavior is isolated by following the evolution of key vibrational features when the C{sub (2)} hydrogen, the proposed binding location of the anion to the imidazolium ring, is replaced by either deuterium or a methyl group (i.e., in the EMMIM{sup +} analogue). Strong features in the ring CH stretching region of the bare ion are traced to Fermi resonances with overtones of lower frequency modes. Upon incorporation into the EMIM{sup +} ⋅ ⋅ ⋅ BF{sub 4}{sup −} ⋅ ⋅ ⋅ EMIM{sup +} ternary complex, the C{sub (2)}H oscillator strength is dramatically increased, accounting for the much more complicated patterns derived from the EMIM{sup +} ring CH stretches in the light isotopomer, which are strongly suppressed in the deuterated analogue. Further changes in the spectra that occur when the C{sub (2)}H is replaced by a methyl group are consistent with BF{sub 4}{sup −} attachment directly to the imidazolium ring in an arrangement that maximizes the electrostatic interaction between the molecular ions.

  12. Applications of functionalized ionic liquids

    Institute of Scientific and Technical Information of China (English)

    LI; Xuehui; ZHAO; Dongbin; FEI; Zhaofu; WANG; Lefu

    2006-01-01

    Recent developments of the synthesis and applications of functionalized ionic liquids(including dual-functionalized ionic liquids) have been highlighted in this review. Ionic liquids are attracting attention as alternative solvents in green chemistry, but as more functionalized ILs are prepared, a greater number of applications in increasingly diverse fields are found.

  13. Application of Ionic Liquids with Carboxyl and Aromatic Ring Conjugated Anions in Dye-Sensitized Solar Cells%阴离子为羧酸根和芳环共轭的离子液体在染料敏化太阳能电池中的应用

    Institute of Scientific and Technical Information of China (English)

    王海; 徐雪青; 史继富; 徐刚

    2013-01-01

      提出了利用p-π共轭效应设计离子液体的方法, p-π共轭效应可以有效分散阴离子的负电荷,降低离子液体中阴阳离子之间的库仑引力,以得到低粘度的离子液体.所设计的离子液体为1-乙基-3-甲基咪唑苯甲酸(EMIB)和1-乙基-3-甲基咪唑异烟酸(EMIIN)(它们的阴离子中羧酸根和芳环为p-π共轭结构),这两种离子液体都达到了较低的粘度(EMIB为42 mPa·s, EMIIN为27 mPa·s).进一步将这两种离子液体做成电解质,应用在染料敏化太阳能电池中,通过优化电解质的组成, EMIB基电解质达到了1.43 mS·cm-1的电导率和1.45×10-7 cm2·s-1的I-3的扩散系数,而EMIIN基电解质的电导率和I-3扩散系数分别为1.63 mS·cm-1和2.01×10-7 cm2·s-1,后者电导性能的提高主要和EMIIN粘度较低有关系.进一步将这两种电解质组装成电池,在300 W·m-2的光强下测得EMIB基电池和EMIIN基电池的效率分别为2.85%和4.30%.%A method of utilizing p-π conjugation effects for obtaining low-viscosity ionic liquids is presented. p-π conjugation effectively disperses anionic charge and reduces Coulombic interactions. Ionic liquids prepared in this study were 1-ethyl-3-methylimidazolium benzoate (EMIB) and 1-ethyl-3-methylimidazolium isonicotinate (EMIIN). They have carboxyl and aromatic ring p-π conjugated anions, and achieve low viscosities of 42 and 27 mPa·s, respectively. EMIB and EMIIN were employed as electrolytes, which were used to construct dye-sensitized solar cel s (DSCs). After optimizing the composition, the ionic conductivity and tri odide ionic diffusion constant for the EMIB-based electrolyte were 1.43 mS·cm-1 and 1.45 × 10-7 cm2·s-1, respectively. For the EMIIN-based electrolyte, the ionic conductivity and tri odide ionic diffusion constant were 1.63 mS·cm-1 and 2.01×10-7 cm2·s-1, respectively. These were higher than the corresponding values for the EMIB-based electrolyte because of EMIINʹs lower

  14. Ionic and Molecular Liquids

    DEFF Research Database (Denmark)

    Chaban, Vitaly V.; Prezhdo, Oleg

    2013-01-01

    Because of their outstanding versatility, room-temperature ionic liquids (RTILs) are utilized in an ever increasing number of novel and fascinating applications, making them the Holy Grail of modern materials science. In this Perspective, we address the fundamental research and prospective...... applications of RTILs in combination with molecular liquids, concentrating on three significant areas: (1) the use of molecular liquids to decrease the viscosity of RTILs; (2) the role of RTIL micelle formation in water and organic solvents; and (3) the ability of RTILs to adsorb pollutant gases. Current...

  15. Cyclic phosphonium ionic liquids

    Directory of Open Access Journals (Sweden)

    Sharon I. Lall-Ramnarine

    2014-01-01

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

  16. Wettability by Ionic Liquids.

    Science.gov (United States)

    Liu, Hongliang; Jiang, Lei

    2016-01-06

    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.

  17. Graphene-ionic liquid composites

    Science.gov (United States)

    Aksay, Ilhan A.; Korkut, Sibel; Pope, Michael; Punckt, Christian

    2016-11-01

    Method of making a graphene-ionic liquid composite. The composite can be used to make elec-trodes for energy storage devices, such as batteries and supercapacitors. Dis-closed and claimed herein is method of making a graphene-ionic liquid com-posite, comprising combining a graphene source with at least one ionic liquid and heating the combination at a temperature of at least about 130 .degree. C.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  19. Electrochemical aspects of ionic liquids

    CERN Document Server

    Ohno, Hiroyuki

    2011-01-01

    The second edition is based on the original book, which has been revised, updated and expanded in order to cover the latest information on this rapidly growing field. The book begins with a description of general and electrochemical properties of ionic liquids and continues with a discussion of applications in biochemistry, ionic devices, functional design and polymeric ionic liquids. The new edition includes new chapters on Li ion Batteries and Actuators, as well as a revision of existing chapters to include a discussion on purification and the effects of impurities, adsorption of ionic liqui

  20. Nanoconfined Ionic Liquids.

    Science.gov (United States)

    Zhang, Shiguo; Zhang, Jiaheng; Zhang, Yan; Deng, Youquan

    2016-12-29

    Ionic liquids (ILs) have been widely investigated as novel solvents, electrolytes, and soft functional materials. Nevertheless, the widespread applications of ILs in most cases have been hampered by their liquid state. The confinement of ILs into nanoporous hosts is a simple but versatile strategy to overcome this problem. Nanoconfined ILs constitute a new class of composites with the intrinsic chemistries of ILs and the original functions of solid matrices. The interplay between these two components, particularly the confinement effect and the interactions between ILs and pore walls, further endows ILs with significantly distinct physicochemical properties in the restricted space compared to the corresponding bulk systems. The aim of this article is to provide a comprehensive review of nanoconfined ILs. After a brief introduction of bulk ILs, the synthetic strategies and investigation methods for nanoconfined ILs are documented. The local structure and physicochemical properties of ILs in diverse porous hosts are summarized in the next sections. The final section highlights the potential applications of nanoconfined ILs in diverse fields, including catalysis, gas capture and separation, ionogels, supercapacitors, carbonization, and lubrication. Further research directions and perspectives on this topic are also provided in the conclusion.

  1. Hydrophobic ionic liquids

    Science.gov (United States)

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

    1998-01-01

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

  2. Ultrasonicwave-assisted extraction of lycopene from fresh tomato with ionic liquid%离子液体在番茄红素提取中的应用研究

    Institute of Scientific and Technical Information of China (English)

    崔萌; 胡乐根; 马停停; 蔡明建; 王秀阁

    2012-01-01

    以1-丁基-3-甲基咪唑四氟硼酸盐([Bmim]BF4)、1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF6)、1-乙基-3-甲基咪唑四氟硼酸盐([Emim]BF4)、1-乙基-3-甲基溴盐([Emim]Br)、1-丁基-3-甲基咪唑硫酸一氢盐([Bmim]HSO4)离子液体为萃取剂,并用超声波辅助萃取新鲜番茄中的番茄红素.对离子液体超声波辅助萃取新鲜番茄中的番茄红素的条件进行了优化,优化后的提取条件为:以[Bmim]BF4为萃取溶剂,离子液体浓度:V乙醇/V[Bmim]BF4=3,在固定超声温度为40℃,超声萃取时间10min,超声波功率380W,料液比1:5 (g/mL)时,效果最佳.%Applying the ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborat ([ Bmim] BF4 ) , 1-butyl-3-methylimidazolium hexafluorophosphate( [Bmim]PF6) ,1-ethyl-3-methylimidazolium tetrafluoroborat( [Emim] BF4) ,1-butyl-3-methylimidazolium bro-mide( [Emim]Br) ,and 1-butyl-3-methylimizolium hydrosulfate( [Bmim]HSO4)as solvents,the ultrasonicwave-assisted solvent extraction of lycopene from fresh tomato were investigated, and the influences of extraction parameters on the extraction yield were discussed. The optimal operating conditions for ultrasonicwave-assisted extraction of lycopene with ionic liquid as solvent was obtained as follows;the suitable solvent used was[Bmim]BF4 with concentration of Vethanol/V[Bmin]BF = 3, ultrasonic temperature was fixed to ,the ultrasonic extraction time was 10 min and the ultrasonicwave power was 380 W.then the extraction effect was excellent

  3. Ionic Liquid Epoxy Resin Monomers

    Science.gov (United States)

    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.

  4. Leaching performance of imidazolium based ionic liquids in the presence of hydrogen peroxide for recovery of metals from brass waste

    Directory of Open Access Journals (Sweden)

    Kilicarslan, Ayfer

    2016-03-01

    Full Text Available The application of ionic liquids (ILs, 1-methylimidazolium hydrogen sulfate (HmimHSO4, 1-ethyl-3-methylimidazolium hydrogen sulfate (HmimHSO4 and 1-butyl-3-methylimidazolium chloride (BmimCl as leaching agents was investigated in the leaching of copper and zinc from brass waste in the presence of an oxidant, hydrogen peroxide (H2O2. Factors that affect copper and zinc dissolution rates such as ionic liquid concentration, time and temperature were investigated. The results indicated that zinc was dissolved in leach solutions with EmimHSO4 and HmimHSO4, completely. Temperature had no considerable influence on copper dissolution rate whilst the rate increased with decreasing IL concentration. In the EmimHSO4 system, higher copper recoveries were achieved with 40% and 60% IL concentrations compared with IL concentrations of 20% and 80% at 40 °C leaching temperature. Copper dissolution rates decreased with EmimHSO4 concentration at 60 °C and 80 °C in the following order; 40% > 20% > 60% > 80%. On the other hand the leaching system with BmimCl generally resulted in poor extractions of copper and zinc.Este trabajo investiga el uso de líquidos iónicos (LIs, hidrogenosulfato de 1-metillimidazolio (HmimHSO4, hidrogenosulfato de 1-etil-3- metilimidazolio (EmimHSO4 y cloruro de 1-butil-1-metilimidazolio (BmimCl, como agentes de lixiviación de cobre y zinc a partir de residuos de latón en presencia de un oxidante, peróxido de hidrógeno (H2O2. Se estudiaron distintos factores que afectan a la velocidad de disolución del cobre y el zinc, como la concentración del líquido iónico, el tiempo y la temperatura. Los resultados indican que el zinc se disuelve completamente en las disoluciones que contienen EmimHSO4 y HmimHSO4. La temperatura no tiene un efecto significativo en la velocidad de disolución del cobre, mientras que dicha velocidad aumenta al disminuir la concentración del líquido iónico. En los sistemas que contienen EmimHSO4, los mejores

  5. Lipid processing in ionic liquids

    DEFF Research Database (Denmark)

    Lue, Bena-Marie; Guo, Zheng; Xu, Xuebing

    2007-01-01

    Ionic liquids (ILs) have been touted as “green” alternatives to traditional molecular solvents and have many unique properties which make them extremely desirable substitutes. Among their most attractive properties are their lack of vapour pressure, broad liquid range, strong solvating power...

  6. Recrystallized quinolinium ionic liquids for electrochemical analysis

    Science.gov (United States)

    Selvaraj, Gowri; Wilfred, Cecilia Devi; Eang, Neo Kian

    2016-11-01

    Ionic liquids have received a lot of attention due to their unique properties. In this work the prospect of quinolinium based ionic liquids as electrolyte for dye sensitised solar cell were tested using cyclic voltammetry. The results have shown electron transfer in the ionic liquid without undergoing any permanent chemical changes. Prior to testing, the ionic liquids were purified through recrystallization as electrochemical properties of ionic liquids are highly dependent on the purity of the ionic liquids. This results have shone new light for this work.

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

    Science.gov (United States)

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

    2012-01-21

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

  8. Fluctuating hydrodynamics for ionic liquids

    Science.gov (United States)

    Lazaridis, Konstantinos; Wickham, Logan; Voulgarakis, Nikolaos

    2017-04-01

    We present a mean-field fluctuating hydrodynamics (FHD) method for studying the structural and transport properties of ionic liquids in bulk and near electrified surfaces. The free energy of the system consists of two competing terms: (1) a Landau-Lifshitz functional that models the spontaneous separation of the ionic groups, and (2) the standard mean-field electrostatic interaction between the ions in the liquid. The numerical approach used to solve the resulting FHD-Poisson equations is very efficient and models thermal fluctuations with remarkable accuracy. Such density fluctuations are sufficiently strong to excite the experimentally observed spontaneous formation of liquid nano-domains. Statistical analysis of our simulations provides quantitative information about the properties of ionic liquids, such as the mixing quality, stability, and the size of the nano-domains. Our model, thus, can be adequately parameterized by directly comparing our prediction with experimental measurements and all-atom simulations. Conclusively, this work can serve as a practical mathematical tool for testing various theories and designing more efficient mixtures of ionic liquids.

  9. Selective Extraction of Bioproducts by Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    王键吉; 裴渊超; 赵扬; 张锁江

    2005-01-01

    Imidazolium based room temperature ionic liquids have been used to extract selectively L-tryptophan from fermentation broth. BF4 anion was found to enhance dramatically the partitioning of L-tryptophan into ionic liquid phase from aqueous solutions.

  10. Externally Wetted Ionic Liquid Thruster

    Science.gov (United States)

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

    2004-10-01

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

  11. Modelling room temperature ionic liquids.

    Science.gov (United States)

    Bhargava, B L; Balasubramanian, Sundaram; Klein, Michael L

    2008-08-07

    Room temperature ionic liquids (IL) composed of organic cations and inorganic anions are already being utilized for wide-ranging applications in chemistry. Complementary to experiments, computational modelling has provided reliable details into the nature of their interactions. The intra- and intermolecular structures, dynamic and transport behaviour and morphologies of these novel liquids have also been explored using simulations. The current status of molecular modelling studies is presented along with the prognosis for future work in this area.

  12. Nanoparticle enhanced ionic liquid heat transfer fluids

    Science.gov (United States)

    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.

  13. Gaseous Hydrocarbon Separations Using Functionalized Ionic Liquids

    OpenAIRE

    2016-01-01

    The functionalization of the side chains on the cation or the anion of an ionic liquid is a common approach to tailor its properties for different processes including the separation of gases. In this paper, we present the current state of the art concerning the usage of ionic liquids for hydrocarbon separations. We also show how the functionalization of ionic liquids or the appropriate anion/cation combinations can contribute to the increase of the performance of the ionic liquids for the sep...

  14. The hype with ionic liquids as solvents

    Science.gov (United States)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

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

  15. Nanoparticles in ionic liquids: interactions and organization.

    Science.gov (United States)

    He, Zhiqi; Alexandridis, Paschalis

    2015-07-28

    Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

  16. An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes

    Directory of Open Access Journals (Sweden)

    N. F. A. Fattah

    2016-06-01

    Full Text Available Solid polymer electrolyte (SPE composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene [P(VdF-HFP] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl imide [EMI-BTI] and graphene oxide (GO was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC. The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD and thermogravimetric analysis (TGA studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge–discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g−1, which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

  17. On the Chemical Stabilities of Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Yen-Ho Chu

    2009-09-01

    Full Text Available Ionic liquids are novel solvents of interest as greener alternatives to conventional organic solvents aimed at facilitating sustainable chemistry. As a consequence of their unusual physical properties, reusability, and eco-friendly nature, ionic liquids have attracted the attention of organic chemists. Numerous reports have revealed that many catalysts and reagents were supported in the ionic liquid phase, resulting in enhanced reactivity and selectivity in various important reaction transformations. However, synthetic chemists cannot ignore the stability data and intermolecular interactions, or even reactions that are directly applicable to organic reactions in ionic liquids. It is becoming evident from the increasing number of reports on use of ionic liquids as solvents, catalysts, and reagents in organic synthesis that they are not totally inert under many reaction conditions. While in some cases, their unexpected reactivity has proven fortuitous and in others, it is imperative that when selecting an ionic liquid for a particular synthetic application, attention must be paid to its compatibility with the reaction conditions. Even though, more than 200 room temperature ionic liquids are known, only a few reports have commented their effects on reaction mechanisms or rate/stability. Therefore, rather than attempting to give a comprehensive overview of ionic liquid chemistry, this review focuses on the non-innocent nature of ionic liquids, with a decided emphasis to clearly illuminate the ability of ionic liquids to affect the mechanistic aspects of some organic reactions thereby affecting and promoting the yield and selectivity.

  18. Measurement of vibrational spectrum of liquid using monochromated scanning transmission electron microscopy-electron energy loss spectroscopy.

    Science.gov (United States)

    Miyata, Tomohiro; Fukuyama, Mao; Hibara, Akihide; Okunishi, Eiji; Mukai, Masaki; Mizoguchi, Teruyasu

    2014-10-01

    Investigations on the dynamic behavior of molecules in liquids at high spatial resolution are greatly desired because localized regions, such as solid-liquid interfaces or sites of reacting molecules, have assumed increasing importance with respect to improving material performance. In application to liquids, electron energy loss spectroscopy (EELS) observed with transmission electron microscopy (TEM) is a promising analytical technique with the appropriate resolutions. In this study, we obtained EELS spectra from an ionic liquid, 1-ethyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C2mim-TFSI), chosen as the sampled liquid, using monochromated scanning TEM (STEM). The molecular vibrational spectrum and the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap of the liquid were investigated. The HOMO-LUMO gap measurement coincided with that obtained from the ultraviolet-visible spectrum. A shoulder in the spectrum observed ∼0.4 eV is believed to originate from the molecular vibration. From a separately performed infrared observation and first-principles calculations, we found that this shoulder coincided with the vibrational peak attributed to the C-H stretching vibration of the [C2mim(+)] cation. This study demonstrates that a vibrational peak for a liquid can be observed using monochromated STEM-EELS, and leads one to expect observations of chemical reactions or aids in the analysis of the dynamic behavior of molecules in liquid. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  19. Ionic Liquids to Replace Hydrazine

    Science.gov (United States)

    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.

  20. Supported Ionic Liquid Phase (SILP) catalysis

    DEFF Research Database (Denmark)

    Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco;

    2006-01-01

    Applications of ionic liquids to replace conventional solvents in homogeneous transition-metal catalysis have increased significantly during the last decade. Biphasic ionic liquid/organic liquid systems offer advantages with regard to product separation, catalyst stability, and recycling but util...

  1. Ionic Liquids: Just Molten Salts After All?

    Directory of Open Access Journals (Sweden)

    Anna K. Croft

    2009-07-01

    Full Text Available While there has been much effort in recent years to characterise ionic liquids in terms of parameters that are well described for molecular solvents, using these to explain reaction outcomes remains problematic. Herein we propose that many reaction outcomes in ionic liquids may be explained by considering the electrostatic interactions present in the solution; that is, by recognising that ionic liquids are salts. This is supported by evidence in the literature, along with studies presented here.

  2. Tailor-made ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Jork, C. [Technische Universitaet Berlin, Strasse des 17. Juni 135, Institut fuer Verfahrenstechnik, Fachgebiet Thermodynamik und Thermische Verfahrenstechnik, 10623 Berlin (Germany); Kristen, C. [Technische Universitaet Berlin, Strasse des 17. Juni 135, Institut fuer Verfahrenstechnik, Fachgebiet Thermodynamik und Thermische Verfahrenstechnik, 10623 Berlin (Germany); Pieraccini, D. [University of Pisa, Dipartimento di Chimica Bioorganica e Biofarmacia, via Bonanno 33, 56126 Pisa (Italy); Stark, A. [Friedrich-Schiller-Universitaet Jena, Institut fuer Technische Chemie und Umweltchemie, Lessingstrasse 12, 07743 Jena (Germany); Chiappe, C. [University of Pisa, Dipartimento di Chimica Bioorganica e Biofarmacia, via Bonanno 33, 56126 Pisa (Italy); Beste, Y.A. [BASF AG, GCT/A-L540, 67056 Ludwigshafen (Germany); Arlt, W. [Universitaet Erlangen/Nuernberg, Lehrstuhl fuer Thermische Verfahrenstechnik, Egerlandstrasse 3, 91058 Erlangen (Germany)]. E-mail: wolfgang.arlt@cbi.uni-erlangen.de

    2005-06-15

    This article presents a first consequent thermodynamic optimization of ionic liquids (IL) as entrainers in the distillative separation of both an azeotropic aqueous (tetrahydrofuran + water) and a close-boiling aromatic test system (methylcyclohexane + toluene) on the basis of COSMO-RS predictions. The use of this method allows for the preselection from the large pool of available IL. Thus, favorable structural variations were identified and used for tailoring IL entrainers. For the prediction of activity coefficients with COSMO-RS, the use of different conformations of the components, derived from conformational analyses, leads to varying results. The simulations showed that the influence of conformations of the volatile components and the ionic liquids depends largely on the type of the phase equilibrium, which is investigated. The approach to tailor ionic liquids as additives for separation science starts with the prediction of the activity coefficients at infinite dilution. The simulation indicated that a higher degree of branching or longer alkyl substituents on the cation, as well as a low nucleophilicity of the anion decreases both selectivity and capacity in the polar test mixture. However, COSMO-RS calculations for the non-polar mixture showed that the selection of an entrainer for this system is more complicated, because - contrarily to (tetrahydrofuran + water) - structural variations of the IL entrainer cause converse changes in selectivity and capacity: while the selectivity for toluene increases with a lower degree of branching and a shorter alkyl substituent of the cation as well as with a lower nucleophilicity of the anion, these properties decrease the capacity. In this work, the most favorable IL entrainers were synthesized and the separation factors of the test systems were experimentally validated at finite dilution.

  3. Improved Ionic Liquids as Space Lubricants Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Ionic liquids are candidate lubricant materials. However for application in low temperature space mechanisms their lubrication performance needs to be enhanced. UES...

  4. Technologies for Developing Predictive Atomistic and Coarse-Grained Force Fields for Ionic Liquid Property Prediction

    Science.gov (United States)

    2008-07-29

    Butanesulfonate (some parameters for 1-ethyl-3-methylimidazolium cation taken from the work of Cadena et al).2 I. Intramolecular terms (bond, angles...parameters for the anions of (A) and (B). Dihedral parameters for the cation of (B) were taken directly from the work of Cadena et al.2 Dihedral...19586. 2 Cadena , C.; Anthony, J. L.; Shah, J. K.; Morrow, T. I.; Brennecke, J. F.; Maginn, E. J. J. Am. Chem. Soc., 2004, 126, 5300 3 Schmidt

  5. Ionic-Liquid-Tethered Nanoparticles: Hybrid Electrolytes

    KAUST Repository

    Moganty, Surya S.

    2010-10-22

    A new class of solventless electrolytes was created by tethering ionic liquids to hard inorganic ZrO2 nanostructures (see picture; NIM=nanoscale ionic material). These hybrid fluids exhibit exceptional redox stability windows, excellent thermal stability, good lithium transference numbers, long-term interfacial stability in the presence of a lithium anode and, when doped with lithium salt, reasonable ionic conductivities.

  6. Quantized friction across ionic liquid thin films

    Science.gov (United States)

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

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

  7. Quantized friction across ionic liquid thin films.

    Science.gov (United States)

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

    2013-10-07

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

  8. Engineered microorganisms having resistance to ionic liquids

    Science.gov (United States)

    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.

  9. Chemical and Electrochemical Studies in Ionic Liquids

    Science.gov (United States)

    1990-01-12

    Electrochemistry and Witchcraft ", Gordon Research Conference on Electrochemistry", Santa Barbara, CA, January, 1985. OR. A. Osteryoung, ’An Introduction to...Temperature Chloroaluminate Ionic Liquids: Chemistry, Electrochemistry and Witchcraft ", Chemistry Department Colloquium, University of Alabama...Tuscaloosa, Alabama, December 1, 1988. OR. A. Osteryoung, "Ambient Temperature Chloroaluminate Ionic Liquids: Chemistry, Electrochemistry and Witchcraft

  10. Facile Synthesis of Ureas in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    Wei Xing QIAN; Feng Yang JU; Yong Min ZHANG; Wei Liang BAO

    2004-01-01

    The reaction of isocyanates with aliphatic and aromatic amines in the 1-n-butyl-3- methylimidazolium tetrafluoroborate (bmimBF4) ionic liquid in good to excellent yields is described. Due to its insolubility, the desired urea solids could be recovered by simple filtration from the ionic liquid after reaction.

  11. Base stable quaternary ammonium ionic liquids

    OpenAIRE

    Lethesh, Kallidanthiyil Chellappan; Dehaen, Wim; Binnemans, Koen

    2014-01-01

    Ionic liquids with the bis(2-ethylhexyl)dimethylammonium cation, [BEDMA]+, were prepared by a halide-free route starting from the readily available secondary amine bis(2-ethylhexyl)amine. The following anions were considered: chloride, bromide, iodide, nitrate, hydrogensulphate, dihydrogenphosphate, formate, acetate, propionate, trifluoroacetate, methyl sulphate, methanesulphonate, tosylate, isonicotinate, nicotinate and picolinate. Several of the compounds are room-temperature ionic liquids,...

  12. Gaseous Hydrocarbon Separations Using Functionalized Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Moura Leila

    2016-03-01

    Full Text Available The functionalization of the side chains on the cation or the anion of an ionic liquid is a common approach to tailor its properties for different processes including the separation of gases. In this paper, we present the current state of the art concerning the usage of ionic liquids for hydrocarbon separations. We also show how the functionalization of ionic liquids or the appropriate anion/cation combinations can contribute to the increase of the performance of the ionic liquids for the separation of gaseous hydrocarbons – either by improving the capacity of the ionic liquid to absorb a given gas or by increasing the selectivity towards a particular hydrocarbon. Original results concerning the usage of olefin-complexing metal salts of lithium (I, nickel (II and copper (II dissolved in ionic liquids for selectively absorbing light olefins are presented. It is observed that the absorption capacity of an imidazolium-based ionic liquid is doubled by the addition of a copper (II salt. This result is compared with the effect of the functionalization of the ionic liquid and the advantages and difficulties of the two approaches are analyzed.

  13. Aqueous solutions of ionic liquids: microscopic assembly

    NARCIS (Netherlands)

    Vicent-Luna, J.M.; Dubbeldam, D.; Gómez-Álvarez, P.; Calero, S.

    2016-01-01

    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

  14. Fast Ignition and Sustained Combustion of Ionic Liquids

    Science.gov (United States)

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

    2016-01-01

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

  15. 离子液体中Lewis酸催化葡萄糖和果糖脱水制备5-羟甲基呋喃甲醛%Dehydration of Glucose and Fructose into 5-Hydroxymethylfurfural Catalyzed by Lewis Acid in Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    田玉奎; 邓晋; 潘涛; 郭庆祥; 傅尧

    2011-01-01

    在离子液体中采用不同的Lewis酸催化葡萄糖和果糖脱水制备5-羟甲基呋喃甲醛(5-HMF).结果表明,CrCln和SnCln均可高效催化葡萄糖转化为5-HMF.另外,Lewis酸的酸性越强,其催化果糖转化为5-HMF的产率越高.镧系金属氯化物在反应中表现出较好的催化活性和产物选择性.同时还研究了离子液体结构对催化反应的影响.结果表明,咪唑型离子液体在葡萄糖转化为5-HMF的反应中表现出明显的奇偶效应,即离子液体支链碳原予数为偶数时,5-HMF产率较高;而在果糖转化为5-HMF的反应中,离子液体的支链烷基长度越短,5-HMF产率越高.在离子液体[C2MIM]Br(溴化1-乙基-3-甲基咪唑)中,SnCl2催化葡萄糖脱水时5-HMF收率为65%,而ErCl3催化果糖得到的5-HMF收率可达92%.%A variety of Lewis acids have been examined for the transformation of glucose and fructose into 5-hydroxymethylfurfural (5-HMF) in ionic liquids (ILs). SnCln and CrCln are effective catalysts for the isomerization, and Lewis acids with strong acidity can facili tate the dehydration of fructose. The influence of ILs structure, including the length of alkyl side chain and halide anions, on the conversion was also studied. A distinct odd-even carbon-atom-number effect is observed in the conversion of glucose to 5-HMF and the imidazolium bromides with short alkyl side-chains can provide a higher yield of 5-HMF from fructose. In the presence of 1-ethyl-3-methylimidazolium bromide ([C2MIM]Br) and SnCl2, the yields of 5-HMF are 65% and 73% from glucose and fructose, respectively.

  16. Ionic liquids in analytical chemistry.

    Science.gov (United States)

    Soukup-Hein, Renee J; Warnke, Molly M; Armstrong, Daniel W

    2009-01-01

    The role of ionic liquids (ILs) in analytical chemistry is increasing substantially every year. A decade ago there were but a handful of papers in this area of research that were considered curiosities at best. Today, those publications are recognized as seminal articles that gave rise to one of the most rapidly expanding areas of research in chemical analysis. In this review, we briefly highlight early work involving ILs and discuss the most recent advances in separations, mass spectrometry, spectroscopy, and electroanalytical chemistry. Many of the most important advances in these fields depend on the development of new, often unique ILs and multifunctional ILs. A better understanding of the chemical and physical properties of ILs is also essential.

  17. Crowned Ionic Liquids for Biomolecular Interaction Analysis.

    Science.gov (United States)

    Tseng, Ming-Chung; Yuan, Tsu-Chun; Li, Zhuo; Chu, Yen-Ho

    2016-11-15

    On the basis of affinity recognition with positively charged side chains in peptides and proteins, a series of crowned 1,2,3-triazolium ionic liquids (CIL 1-6) was developed and found to be capable of quantitatively extracting peptides and proteins from the aqueous layer into the ionic liquid phase. All of the synthesized CIL 1-6 are liquid at room temperature. This is the first example of biomolecular recognition of both lysine- and arginine-containing peptides and proteins by CILs in pure ionic liquid phase.

  18. A highly viscous imidazolium ionic liquid inside carbon nanotubes.

    Science.gov (United States)

    Ohba, Tomonori; Chaban, Vitaly V

    2014-06-12

    We report a combined experimental (X-ray diffraction) and theoretical (molecular dynamics, hybrid density functional theory) study of 1-ethyl-3-methylimidazolium chloride, [C2C1MIM][Cl], inside carbon nanotubes (CNTs). We show that despite its huge viscosity [C2C1MIM][Cl] readily penetrates into 1-3 nm wide CNTs at slightly elevated temperatures (323-363 K). Molecular simulations were used to assign atom-atom peaks. Experimental and simulated structures of RTIL inside CNT and in bulk phase are in good agreement. We emphasize a special role of the CNT-chloride interactions in the successful adsorption of [C2C1MIM][Cl] on the inner sidewalls of 1-3 nm carbon nanotubes.

  19. A Highly Viscous Imidazolium Ionic Liquid inside Carbon Nanotubes

    DEFF Research Database (Denmark)

    Ohba, T.; Chaban, Vitaly V.

    2014-01-01

    We report a combined experimental (X-ray diffraction) and theoretical (molecular dynamics, hybrid density functional theory) study of 1-ethyl-3-methylimidazolium chloride, [C2C1MIM][Cl], inside carbon nanotubes (CNTs). We show that despite its huge viscosity [C2C1MIM][Cl] readily penetrates into 1......-3 nm wide CNTs at slightly elevated temperatures (323-363 K). Molecular simulations were used to assign atom-atom peaks. Experimental and simulated structures of RTIL inside CNT and in bulk phase are in good agreement. We emphasize a special role of the CNT-chloride interactions in the successful...... adsorption of [C2C1MIM][Cl] on the inner sidewalls of 1-3 nm carbon nanotubes....

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

    Science.gov (United States)

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

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

  1. Application of Ionic Liquids in Hydrometallurgy

    Directory of Open Access Journals (Sweden)

    Jesik Park

    2014-08-01

    Full Text Available 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.

  2. The structure of ionic liquids

    CERN Document Server

    Gontrani, Lorenzo

    2014-01-01

    This volume describes the most recent findings on the structure of ILs interpreted through cutting-edge experimental and theoretical methods. Research in the field of ionic liquids (ILs) keeps a fast and steady pace. Since these new-generation molten salts first appeared in the chemistry and physics landscape, a large number of new compounds has been synthesized. Most of them display unexpected behaviour and possess stunning properties. The coverage in this book ranges from the mesoscopic structure of ILs to their interaction with proteins. The reader will learn how diffraction techniques (small and large angle X-Ray and neutron scattering, powder methods), X-Ray absorption spectroscopies (EXAFS/XANES), optical methods (IR, RAMAN), NMR and calorimetric methods can help the study of ILs, both as neat liquids and in mixtures with other compounds. It will enable the reader to choose the best method to suit their experimental needs. A detailed survey of theoretical methods, both quantum-chemical and classical, ...

  3. Ionic liquids for rechargeable lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Ionic Liquid Fuels for Chemical Propulsion

    Science.gov (United States)

    2016-10-31

    energetic materials; chemical kinetics ; hypergolic fuels; salts; ligands; lithium; borohydrides; density functional theory; flammability 16. SECURITY...continuum model  DFT  density functional theory  DME   dimethoxethane  DNB  1,5‐dinitrobiuret  GIL   generalized ionic liquid  He  helium  IL  ionic liquid... kinetics and reaction dynamics involved in the hypergolic and catalytic ignition of ionic liquid propellants with the purpose of identifying key

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Eero eSalminen

    2014-02-01

    Full Text Available 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.

  7. Ionic liquid polyoxometalates as light emitting materials

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz-acosta, Denisse [Los Alamos National Laboratory; Del Sesto, Rico E [Los Alamos National Laboratory; Scott, Brian [Los Alamos National Laboratory; Bennett, Bryan L [Los Alamos National Laboratory; Purdy, Geraldine M [Los Alamos National Laboratory; Muenchausen, Ross E [Los Alamos National Laboratory; Mc Kigney, Edward [Los Alamos National Laboratory; Gilbertson, Robert [Los Alamos National Laboratory

    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.

  8. Ionic Liquid Epoxy Composite Cryotanks Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The objective of this work is to determine the optimal process for manufacturing lightweight linerless cryogenic storage tanks using ionic liquid epoxy composite...

  9. Modeling electrokinetics in ionic liquids: General

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chao [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA USA; Bao, Jie [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA USA; Pan, Wenxiao [Department of Mechanical Engineering, University of Wisconsin-Madison, Madison WI USA; Sun, Xin [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA USA

    2017-04-07

    Using direct numerical simulations we provide a thorough study on the electrokinetics of ionic liquids. In particular, the modfied Poisson-Nernst-Planck (MPNP) equations are solved to capture the crowding and overscreening effects that are the characteristics of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the MPNP equations are coupled with the Navier-Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel plates, charging dynamics in a 2D straight-walled pore, electro-osmotic ow in a nano-channel, electroconvective instability on a plane ion-selective surface, and electroconvective ow on a curved ion-selective surface. We discuss how the crowding and overscreening effects and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems.

  10. Selective gas absorption by ionic liquids

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Kegnæs, Søren; Due-Hansen, Johannes;

    2010-01-01

    Reversible absorption performance for the flue gas components CO 2, NO and SO2 has been tested for several different ionic liquids (ILs) at different temperatures and flue gas compositions. Furthermore, different porous, high surface area carriers have been applied as supports for the ionic liquids...... to obtain Supported Ionic Liquid-Phase (SILP) absorber materials. The use of solid SILP absorbers with selected ILs were found to significantly improve the absorption capacity and sorption dynamics at low flue gas concentration, thus making the applicability of ILs viable in technical, continuous flow...... processes for flue gas cleaning. The results show that CO 2, NO and SO2 can be reversible and selective absorbed using different ILs and that Supported Ionic Liquid-Phase (SILP) absorbers are promising materials for industrial flue gas cleaning. Absorption/desorption dynamics can be tuned by temperatures...

  11. Polarization versus Temperature in Pyridinium Ionic Liquids

    DEFF Research Database (Denmark)

    Chaban, V. V.; Prezhdo, O. V.

    2014-01-01

    Electronic polarization and charge transfer effects play a crucial role in thermodynamic, structural, and transport properties of room-temperature ionic liquids (RTILs). These nonadditive interactions constitute a useful tool for tuning physical chemical behavior of RTILs. Polarization and charge...

  12. Phosphonium-based ionic liquids and uses

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Superbase-derived protic ionic liquids

    Science.gov (United States)

    Dai, Sheng; Luo, Huimin; Baker, Gary A.

    2013-09-03

    Protic ionic liquids having a composition of formula (A.sup.-)(BH.sup.+) wherein A.sup.- is a conjugate base of an acid HA, and BH.sup.+ is a conjugate acid of a superbase B. In particular embodiments, BH.sup.+ is selected from phosphazenium species and guanidinium species encompassed, respectively, by the general formulas: ##STR00001## The invention is also directed to films and membranes containing these protic ionic liquids, with particular application as proton exchange membranes for fuel cells.

  14. Ionic liquids in the synthesis of nanoobjects

    Energy Technology Data Exchange (ETDEWEB)

    Tarasova, Natalia P; Smetannikov, Yurii V; Zanin, A A [Institute of Chemistry and Problems of Sustainable Development D.I.Mendeleev University of Chemical Technology of Russia (Russian Federation)

    2010-08-12

    Data on the usage of the novel green solvents, ionic liquids, in the synthesis of nanoobjects and their stabilization are considered. The information is structured according to the resulting products of the synthetic processes: nanoparticles of noble metals, nanoparticles of non-metals, nanoparticles of metal oxides and chalcogenides, nanocomposites, and highly dispersed polymers. The conclusion is made that the ionic liquids might determine the structure and the properties of the nanoobjects, thus opening new fundamental and technological horizons in nanochemistry.

  15. Ionic liquids in the synthesis of nanoobjects

    Science.gov (United States)

    Tarasova, Natalia P.; Smetannikov, Yurii V.; Zanin, A. A.

    2010-08-01

    Data on the usage of the novel green solvents, ionic liquids, in the synthesis of nanoobjects and their stabilization are considered. The information is structured according to the resulting products of the synthetic processes: nanoparticles of noble metals, nanoparticles of non-metals, nanoparticles of metal oxides and chalcogenides, nanocomposites, and highly dispersed polymers. The conclusion is made that the ionic liquids might determine the structure and the properties of the nanoobjects, thus opening new fundamental and technological horizons in nanochemistry.

  16. The Solubility Parameters of Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Andrzej Marciniak

    2010-04-01

    Full Text Available 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.

  17. Thermodynamic Properties of Caprolactam Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    JIANG Lu; BAI Liguang; ZHU Jiqin; CHEN Biaohua

    2013-01-01

    A series of caprolactam ionic liquids (ILs) containing incorporated halide anions were synthesized.Their physical properties,such as melting points,heats of fusion and heat capacities,were measured by differential scanning calorimeter (DSC).The results indicate that these ionic liquids exhibit proper melting points,high value of heats of fusion,and satisfying heat capacities which are suitable for thermal energy storage applications.

  18. Study of thioglycosylation in ionic liquids

    Directory of Open Access Journals (Sweden)

    Ragauskas Arthur

    2006-06-01

    Full Text Available Abstract A novel, green chemistry, glycosylation strategy was developed based upon the use of ionic liquids. Research studies demonstrated that thiomethyl glycosides could readily be activated with methyl trifluoromethane sulfonate, using 1-butyl-3-methylimidazolium tetrafluoroborate as a solvent. This green chemistry glycosylation strategy provided disaccharides with typical yields averaging 75%. The ionic liquid solvent could be readily reused for five sequential glycosylation reactions with no impact on product yield.

  19. Interaction of Novel Ionic Liquids with Soils

    OpenAIRE

    2013-01-01

    With the constant development of new ionic liquids, the understanding of the chemical fate of these compounds also needs to be updated. To this effect, the interaction of a number of novel ionic liquids with soils was determined. Therefore, three novel headgroups (ammonium, phosphonium, or pyrrolidinium) with single or quaternary substitution were tested on a variety of soils with high-to-low organic matter content and high-to-low cation exchange capacity, thereby trying to capture the full r...

  20. Supported ionic liquid membrane in membrane reactor

    Science.gov (United States)

    Makertihartha, I. G. B. N.; Zunita, M.; Dharmawijaya, P. T.; Wenten, I. G.

    2017-01-01

    Membrane reactor is a device that integrates membrane based separation and (catalytic) chemical reaction vessel in a single device. Ionic liquids, considered to be a relatively recent magical chemical due to their unique properties, have a large variety of applications in all areas of chemical industries. Moreover, the ionic liquid can be used as membrane separation layer and/or catalytically active site. This paper will review utilization of ionic liquid in membrane reactor related applications especially Fischer-Tropsch, hydrogenation, and dehydrogenation reaction. This paper also reviews about the capability of ionic liquid in equilibrium reaction that produces CO2 product so that the reaction will move towards the product. Water gas shift reaction in ammonia production also direct Dimethyl Ether (DME) synthesis that produces CO2 product will be discussed. Based on a review of numerous articles on supported ionic liquid membrane (SILM) indicate that ionic liquids have the potential to support the process of chemical reaction and separation in a membrane reactor.

  1. Prediction of gas solubilities in ionic liquids.

    Science.gov (United States)

    Oliferenko, Alexander A; Oliferenko, Polina V; Seddon, Kenneth R; Torrecilla, José S

    2011-10-14

    Ionic liquids (of which it is estimated that there are at least one million simple fluids) generate a rich chemical space, which is now just at the beginning of its systematic exploration. Many properties of ionic liquids are truly unique and, which is more important, can be finely tuned. Differential solubility of industrial chemicals in ionic liquids is particularly interesting, because it can be a basis for novel, efficient, environmentally friendly technologies. Given the vast number of potential ionic liquids, and the impossibility of a comprehensive empirical exploration, it is essential to extract the maximum information from extant data. We report here some computational models of gas solubility. These multiple regression- and neural network-based models cover a chemical space spanned by 48 ionic liquids and 23 industrially important gases. Molecular polarisabilities and special Lewis acidity and basicity descriptors calculated for the ionic liquid cations and anions, as well as for the gaseous solutes, are used as input parameters. The quality of fit "observed versus predicted Henry's law constants" is particularly good for the neural network model. Validation was established with an external dataset, again with a high quality fit. In contrast to many other neural network models published, our model is no "black box", since contributions of the parameters and their nonlinearity characteristics are calculated and analysed.

  2. Aqueous Solutions of Ionic Liquids: Microscopic Assembly.

    Science.gov (United States)

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

    2016-02-01

    Aqueous solutions of ionic liquids are of special interest, due to the distinctive properties of ionic liquids, in particular, their amphiphilic character. A better understanding of the structure-property relationships of such systems is hence desirable. One of the crucial molecular-level interactions that influences the macroscopic behavior is hydrogen bonding. In this work, we conduct molecular dynamics simulations to investigate the effects of ionic liquids on the hydrogen-bond network of water in dilute aqueous solutions of ionic liquids with various combinations of cations and anions. Calculations are performed for imidazolium-based cations with alkyl chains of different lengths and for a variety of anions, namely, [Br](-), [NO3](-), [SCN](-) [BF4](-), [PF6](-), and [Tf2N](-). 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 [Tf2N](-) were found to be the most hydrophilic and hydrophobic anions, respectively. Conversely, the cation chain length did not influence the results.

  3. A novel family of green ionic liquids with surface activities

    Institute of Scientific and Technical Information of China (English)

    ZHANG HaiBo; ZHOU XiaoHai; DONG JinFeng; ZHANG GaoYong; WANG CunXin

    2007-01-01

    Ionic liquids have many unique properties as a new and remarkable class of environmental benign solvents, which promises widespread applications in industry and other areas. However, the ionic liquids with surface activity are rarely reported. In this work, a series of novel ionic liquids was synthesized by using N-methyl-2-pyrrolidone and alkyl bromide. The physical properties of this family of ionic liquids have been characterized, which shows that these compounds have ionic liquids characteristics,surface activity and biocompatibility.

  4. Ionic liquids--an overview.

    Science.gov (United States)

    Jenkins, Harry Donald Brooke

    2011-01-01

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

  5. Ionic liquid processing of cellulose.

    Science.gov (United States)

    Wang, Hui; Gurau, Gabriela; Rogers, Robin D

    2012-02-21

    Utilization of natural polymers has attracted increasing attention because of the consumption and over-exploitation of non-renewable resources, such as coal and oil. The development of green processing of cellulose, the most abundant biorenewable material on Earth, is urgent from the viewpoints of both sustainability and environmental protection. The discovery of the dissolution of cellulose in ionic liquids (ILs, salts which melt below 100 °C) provides new opportunities for the processing of this biopolymer, however, many fundamental and practical questions need to be answered in order to determine if this will ultimately be a green or sustainable strategy. In this critical review, the open fundamental questions regarding the interactions of cellulose with both the IL cations and anions in the dissolution process are discussed. Investigations have shown that the interactions between the anion and cellulose play an important role in the solvation of cellulose, however, opinions on the role of the cation are conflicting. Some researchers have concluded that the cations are hydrogen bonding to this biopolymer, while others suggest they are not. Our review of the available data has led us to urge the use of more chemical units of solubility, such as 'g cellulose per mole of IL' or 'mol IL per mol hydroxyl in cellulose' to provide more consistency in data reporting and more insight into the dissolution mechanism. This review will also assess the greenness and sustainability of IL processing of biomass, where it would seem that the choices of cation and anion are critical not only to the science of the dissolution, but to the ultimate 'greenness' of any process (142 references).

  6. Water Contaminant Mitigation in Ionic Liquid Propellant

    Science.gov (United States)

    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.

  7. Supported ionic liquid-phase (SILP) catalysis

    DEFF Research Database (Denmark)

    Riisager, Anders; Fehrmann, Rasmus; Wasserscheid, P.

    2005-01-01

    The concept of supported ionic liquid-phase (SILP) catalysis has been demonstrated for gas- and liquid-phase continuous fixed-bed reactions using rhodium phosphine catalyzed hydroformylation of propene and 1-octene as examples. The nature of the support had important influence on both the catalytic...

  8. The Research Progress of CO2 Capture with Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    赵志军; 董海峰; 张香平

    2012-01-01

    Due to their negligible volatility, reasonable thermal stability, strong dissolubility, wide liquid range and tunability of structure and property, ionic liquids have been regarded as emerging candidate reagents for CO2 cap- ture from industries gases. In this review, the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids, supported ionic-liquids membranes, polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed. Discussion of relevant research fields was presented and the future developments were suggested.

  9. TETRAALKYLPHOSPHONIUM POLYOXOMETALATES AS NOVEL IONIC LIQUIDS.

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Functional ionic liquids; Funktionelle ionische Fluessigkeiten

    Energy Technology Data Exchange (ETDEWEB)

    Baecker, Tobias

    2012-07-01

    In the thesis at hand, new functional ionic liquids were investigated. Main focus was attended to their structure property relations and the structural features leading to a decrease of the melting point. New compounds of the type 1-butyl-3-methylimidazolium tris(N,Ndialkyldithiocarbamato) uranylate with variously substituated dithiocarbamato ligands were synthesized and characterized. Ligands with asymmetrical substitution pattern proved to be most suitable for ionic liquid formation. The single-crystal X-ray structures revealed the interactions in the solid state. Here, the first spectroscopic investigation of the U-S bond in sulfur donated uranyl complexes, up to now only observed in single-crystal X-ray structures, is presented, and the participation of the uranium f-orbitals is shown by theoretical calculations. Electrochemical investigations showed the accessibility of the respective U{sup V}O{sub 2}{sup +} compounds. As well, ionic liquids with [FeCl{sub 4}]{sup -} and [Cl{sub 3}FeOFeCl{sub 3}]{sup 2-} as anion were synthesized. Both of these anions contain high-spin Fe(III) centres in distorted tetrahedral environment, but exhibit different magnetic behaviour. The tetrachloroferrates show the usual paramagnetism, the m-oxobis(trichloroferrate) exhibits unexpectedly strong antiferromagnetic coupling, as was observed by NMR experiments and susceptibility measurements. To investigate structure-property relations in functionalized ionic liquids, a set of protic, primary alkylammonium and aprotic, quarternary trimethylalkylammonium based ionic liquids was synthesized, and characterized. The length of the alkyl chain was systematically varied, and all compounds were synthesized with and without hydroxyl group, as well as formate and bis(triflyl)amide salts, aiming at getting insight into the influence of the different structure parts on the respective ionic liquid's properties.

  11. Structure of room temperature ionic liquids

    Science.gov (United States)

    Yethiraj, Arun

    2016-10-01

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

  12. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air

    OpenAIRE

    2016-01-01

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

  13. Ionic Liquids in Lithium-Ion Batteries.

    Science.gov (United States)

    Balducci, Andrea

    2017-04-01

    Lithium-ion batteries are among the most widespread energy storage devices in our society. In order to introduce these devices in new key applications such as transportation, however, their safety and their operative temperature range need to be significantly improved. These improvements can be obtained only by developing new electrolytes. Ionic liquids are presently considered among the most attractive electrolytes for the development of advanced and safer lithium-ion batteries. In this manuscript, the use of various types of ionic liquids, e.g. aprotic and protic, in lithium-ion batteries is considered. The advantages and the limits associated to the use of these innovative electrolytes are critically analysed.

  14. Ionic Liquids for Advanced Materials

    Science.gov (United States)

    2008-12-01

    developed characterization set-ups for the electromechanical responses of conductive network/ ionomer composite (CNIC). The overall research goal... glass transition temperature (Tg) with an increase in dielectric constant and ion content. ILs uniquely combine high dielectric constant, low...from 230-440%. Dissociation of ionic aggregates was observed at 85-88 °C in DMA experiments, and the glass transition temperatures increased with

  15. Ionic liquid-nanoparticle hybrid electrolytes

    KAUST Repository

    Lu, Yingying

    2012-01-01

    We investigate physical and electrochemical properties of a family of organic-inorganic hybrid electrolytes based on the ionic liquid 1-methyl-3-propylimidazolium bis(trifluoromethanesulfone) imide covalently tethered to silica nanoparticles (SiO 2-IL-TFSI). The ionic conductivity exhibits a pronounced maximum versus LiTFSI composition, and in mixtures containing 13.4 wt% LiTFSI, the room-temperature ionic conductivity is enhanced by over 3 orders of magnitude relative to either of the mixture components, without compromising lithium transference number. The SiO 2-IL-TFSI/LiTFSI hybrid electrolytes are thermally stable up to 400°C and exhibit tunable mechanical properties and attractive (4.25V) electrochemical stability in the presence of metallic lithium. We explain these observations in terms of ionic coupling between counterion species in the mobile and immobile (particle-tethered) phases of the electrolytes. © 2012 The Royal Society of Chemistry.

  16. Applications of ionic liquids in polymer science and technology

    CERN Document Server

    2015-01-01

    This book summarizes the latest knowledge in the science and technology of ionic liquids and polymers in different areas. Ionic liquids (IL) are actively being investigated in polymer science and technology for a number of different applications. In the first part of the book the authors present the particular properties of ionic liquids as speciality solvents. The state-of-the art in the use of ionic liquids in polymer synthesis and modification reactions including polymer recycling is outlined. The second part focuses on the use of ionic liquids as speciality additives such as plasticizers or antistatic agents.  The third part examines the use of ionic liquids in the design of functional polymers (usually called polymeric ionic liquids (PIL) or poly(ionic liquids)). Many important applications in diverse scientific and industrial areas rely on these polymers, like polymer electrolytes in electrochemical devices, building blocks in materials science, nanocomposites, gas membranes, innovative anion sensitive...

  17. Physical chemistry of reaction dynamics in ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Maroncelli, Mark [Pennsylvania State Univ., University Park, PA (United States)

    2016-10-02

    Work completed over the past year mainly involves finishing studies related to solvation dynamics in ionic liquids, amplifying and extending our initial PFG-NMR work on solute diffusion, and learning how to probe rotational dynamics in ionic liquids.

  18. Physical Chemistry of Reaction Dynamics in Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Maroncelli, Mark [Pennsylvania State Univ., University Park, PA (United States)

    2016-10-02

    Work completed over the past year mainly involves finishing studies related to solvation dynamics in ionic liquids, amplifying and extending our initial PFG-NMR work on solute diffusion, and learning how to probe rotational dynamics in ionic liquids.

  19. CPE OF URANIUM (VI USING IONIC LIQUID

    Directory of Open Access Journals (Sweden)

    SANAA NAÏT-TAHAR

    2016-07-01

    Full Text Available Cloud point extraction (CPE was used to extract uranium (VI from an aqueous solution in acetate media. The methodology used is based on the formation of uranyl-ionic liquid (I complexes and uranyl-D2EHPA soluble in a micellar phase of non-ionic surfactant (Triton X-100. The uranium (VI complexes are then extracted into the surfactant-rich phase at ambient temperature. The ionic liquid (IL used as a chelating agent was synthesized and characterized in this study. It is composed of N-butyl N’-triethoxy methyl imidazolium cation and diethylhexylphosphate (D2EHPA-H as anion. The effect of the IL on the extraction efficiency was studied in presence and in absence of IL’s cation in acetate medium.

  20. VOC and HAP recovery using ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    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

  1. Synthesis, characterization and thermal properties of thiosalicylate ionic liquids

    Indian Academy of Sciences (India)

    Cecilia Devi Wilfred; Fadwa Babiker Mustafa

    2013-11-01

    In an attempt to produce new functionalized ionic liquids, a series of thiosalicylate ionic liquids based on imidazolium, ammonium, phosphonium, choline and pyrrolidinium cations were synthesized. The compounds were characterized by Infra Red (IR), Nuclear Magnetic Resonance (NMR) and mass spectra (ESI-MS). Their glass-transition temperatures, melting points and decomposition temperatures have been measured. Physicochemical properties of ionic liquids are influenced by alkyl chain length and nature of the cation of ionic liquids.

  2. Application of Ionic Liquids in Amperometric Gas Sensors.

    Science.gov (United States)

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

    2016-01-01

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

  3. Characterization and Functionality of Immidazolium Ionic Liquids Modified Magnetic Nanoparticles

    OpenAIRE

    Ying Li; Ning Tang; Fuyuhiko Inagaki; Chisato Mukai; Kazuichi Hayakawa

    2013-01-01

    1,3-Dialkylimidazolium-based ionic liquids were chemically synthesized and bonded on the surface of magnetic nanoparticles (MNPs) with easy one-step reaction. The obtained six kinds of ionic liquid modified MNPs were characterized with transmission electron microscopy, thermogravimetric analysis, magnetization, and FTIR, which owned the high adsorption capacity due to the nanometer size and high-density modification with ionic liquids. Functionality of MNPs with ionic liquids greatly influenc...

  4. Solvation and Reaction in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Maroncelli, Mark

    2015-01-15

    The long-range goal of our DOE-sponsored research is to obtain a fundamental understanding of solvation effects on photo-induced charge transfer and related processes. Much of the focus during the past funding period has been on studies of ionic liquids and on characterizing various reactions with which to probe the nature of this interesting new solvent medium.

  5. Vaporisation of a dicationic ionic liquid.

    Science.gov (United States)

    Lovelock, Kevin R J; Deyko, Alexey; Corfield, Jo-Anne; Gooden, Peter N; Licence, Peter; Jones, Robert G

    2009-02-02

    Highest heat of vaporization yet: The dicationic ionic liquid [C(3)(C(1)Im)(2)][Tf(2)N](2) evaporates as a neutral ion triplet. These neutral ion triplets can then be ionised to form singly and doubly charged ions. The mass spectrum exhibits the dication attached to one remaining anion, and the naked dication itself (see picture).

  6. Catalytic Alkene Metathesis in Ionic Liquids

    Science.gov (United States)

    Fischmeister, Cédric

    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.

  7. Reactions of Starch in Ionic Liquids

    Science.gov (United States)

    We found that starches are found to be soluble at 80 ºC in ionic liquids such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-butyl-3-methylimidazolium dicyanamide (BMIMdca) in concentration up to 10% (w/w). Higher concentrations of biopolymers in these novel solvents resulted in solutions w...

  8. Photo-degradation of imidazolium ionic liquids

    OpenAIRE

    Katoh, Ryuzi; Takahashi, Kenji

    2009-01-01

    Degradation of imidazolium ionic liquid, [bmim+][TFSA-] and iodide solution of [bmim+][TFSA-] by UV-laser irradiation has been studied through ground-state absorption and transient absorption spectroscopy. We found that excited state [bmim+]* undergoes degradation efficiently. © 2009 Elsevier Ltd. All rights reserved.

  9. Esterification of Starch in Ionic Liquids

    Science.gov (United States)

    We shall discuss the use of various ionic liquids in the preparation of starch esters. Starch was reacted with vinyl acetate in different 1-butyl-3-methylimidazolium (bmim) salts as solvents in an effort to produce starches with different acetylation patterns. Overall degree of substitution (DS) w...

  10. Potentiostat for Characterizing Microstructures at Ionic Liquid/Electrode Interfaces

    Science.gov (United States)

    2015-10-10

    Characterizing Microstructures at Ionic Liquid /Electrode Interfaces Report Title This report details the procurement and integration of a multichannel...Haverhals, “Microstructure at the Ionic Liquid /Electrode Interface ”, 226th ECS Meeting, 8 October, 2014, Cancun, Mexico. (c) Presentations Received Paper...Technology Transfer FINAL REPORT “Potentiostat for Characterizing Microstructures at Ionic Liquid /Electrode Interfaces ” Proposal #: 66259CHRI

  11. Synthesis of electroactive ionic liquids for flow battery applications

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-15

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

  13. Recent advances of ionic liquids and polymeric ionic liquids in capillary electrophoresis and capillary electrochromatography.

    Science.gov (United States)

    Tang, Sheng; Liu, Shujuan; Guo, Yong; Liu, Xia; Jiang, Shengxiang

    2014-08-29

    Ionic liquids (ILs) and polymeric ionic liquids (PILs) with unique and fascinating properties have drawn considerable interest for their use in separation science, especially in chromatographic techniques. In this article, significant contributions of ILs and PILs in the improvement of capillary electrophoresis and capillary electrochromatography are described, and a specific overview of the most relevant examples of their applications in the last five years is also given. Accordingly, some general conclusions and future perspectives in these areas are discussed.

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

    Science.gov (United States)

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

    2016-08-03

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

  15. Ionic Liquids and Poly(ionic liquid)s for Morphosynthesis of Inorganic Materials.

    Science.gov (United States)

    Gao, Min-Rui; Yuan, Jiayin; Antonietti, Markus

    2016-10-06

    Ionic liquids (ILs) are new, innovative ionic solvents with rich physicochemical properties and intriguing pre-organized solvent structures; these materials offer great potential to impact across versatile areas of scientific research, for example, synthetic inorganic chemistry. Recent use of ILs as precursors, templates, and solvents has led to inorganic materials with tailored sizes, dimensionalities, morphologies, and functionalities that are difficult to obtain, or even not accessible, by using conventional solvents. Poly(ionic liquid)s (PILs) polymerized from IL monomers also raise the prospect of modifying nucleation, growth, and crystallization of inorganic objects, shedding light on the synthesis of a wide range of new materials. Here we survey recent key progress in using ILs and PILs in the field of synthetic inorganic chemistry. As well as highlighting the unique features of ILs and PILs that enable advanced synthesis, the effects of adding other solvents to the final products, along with the emerging applications of the created inorganic materials will be discussed. We finally provide an outlook on several development opportunities that could lead to new advancements of this exciting research field.

  16. Hydrogen production from glucose in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Assenbaum, D.W.; Taccardi, N.; Berger, M.E.M.; Boesmann, A.; Enzenberger, F.; Woelfel, R.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer chemische Reaktionstechnik

    2010-07-01

    technologies suffer from the fact that the overall reaction rates are often restricted by mass and heat transport problems. Lastly, there are severe limitations concerning the feedstock selection as for some important substrates, such as e.g. glucose, the process can only be operated in very diluted systems to avoid rapid tar formation [22,23,24]. In this contribution we describe for the first time a catalytic reaction system producing hydrogen from glucose in astonishingly high selectivities using a single reaction step under very mild conditions. The catalytic reaction system is characterized by its homogeneous nature and comprises a Ru-complex catalyst dissolved and stabilized in an ionic liquid medium. Ionic liquids are salts of melting points below 100 C [25]. These liquid materials have attracted much interest in the last decade as solvents for catalytic reactions [26] and separation technologies (extraction, distillation) [27,28,29,30,31,32]. Besides, these liquids have found industrial applications as process fluids for mechanic [33] and electrochemical applications [34]. Finally, from the pioneering work of Rogers and co-workers, it is known that ionic liquids are able to dissolve significant amounts of water-insoluble biopolymers (such as e.g. cellulose and chitin)[35] and even complex biopolymer mixtures, such as e.g. wood, have been completely dissolved in some ionic liquids [36]. In our specific application, the role of the ionic liquid is threefold: a) the ionic liquid dissolves the carbohydrate starting material thus expanding the range of applicable carbohydrate to water insoluble polymers; b) the ionic liquid provides a medium to dissolve and stabilize the catalyst; c) the ionic liquid dissolves hydrogen at a very low level, so inhibiting any possible collateral hydrogen-consuming process (detailed investigation of the hydrogen solubility in ionic liquids have been reported by e.g. Brennecke and coworkers [37]). (orig.)

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

    Science.gov (United States)

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

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

  18. Distinct difference in ionic transport behavior in polymer electrolytes depending on the matrix polymers and incorporated salts.

    Science.gov (United States)

    Seki, Shiro; Susan, Md Abu Bin Hasan; Kaneko, Taketo; Tokuda, Hiroyuki; Noda, Akihiro; Watanabe, Masayoshi

    2005-03-10

    Two different electrolyte salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and a room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), were incorporated into network polymers to obtain ion-conductive polymer electrolytes. Network polymers of poly(ethylene oxide-co-propylene oxide) (P(EO/PO)) and poly(methyl methacrylate) (PMMA) were chosen as matrixes for LiTFSI and EMITFSI, respectively. Both of the polymer electrolytes were single-phase materials and were completely amorphous. Ionic conductivity of the polymer electrolytes was measured over a wide temperature range, with the lowest temperatures close to or below the glass transition temperatures (Tg). The Arrhenius plots of the conductivity for both of the systems exhibited positively curved profiles and could be well fit to the Vogel-Tamman-Fulcher (VTF) equation. The conductivity of the PMMA/EMITFSI electrolytes was higher at most by 3 orders of magnitude than that of the LiTFSI/P(EO/ PO) electrolytes at ambient temperature. When the ideal glass transition temperature, T0 (one of the VTF fitting parameters), was compared with the Tg, a difference in the ionic conduction was apparent in these systems. In the P(EO/PO)/LiTFSI electrolytes, the T0 and Tg increased in parallel with salt concentration and the T0 was lower than the Tg by ca. 50 degrees C. On the contrary, the difference between the T0 and the Tg increased with increasing content of PMMA in the PMMA/EMITFSI electrolytes, with the observed difference in the concentration range studied reaching up to ca. 100 degrees C. The conductivity at the Tg, sigma(Tg), for the LiTFSI/P(EO/PO) electrolytes was on the order of 10(-14-)10(-13) S cm(-1) and increased with increasing salt concentration, whereas that for the PMMA/EMITFSI polymer electrolytes reached 10(-7) S cm(-1) when the concentration of PMMA was high. The ion transport mechanism was discussed in terms of the concepts of coupling

  19. A novel family of green ionic liquids with surface activities

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Ionic liquids have many unique properties as a new and remarkable class of environmental benign solvents,which promises widespread applications in industry and other areas. However,the ionic liq-uids with surface activity are rarely reported. In this work,a series of novel ionic liquids was synthe-sized by using N-methyl-2-pyrrolidone and alkyl bromide. The physical properties of this family of ionic liquids have been characterized,which shows that these compounds have ionic liquids characteristics,surface activity and biocompatibility.

  20. Biocatalysis in ionic liquids - advantages beyond green technology.

    Science.gov (United States)

    Park, Seongsoon; Kazlauskas, Romas J

    2003-08-01

    In recent years researchers have started to explore a particular class of organic solvents called room temperature ionic liquids - or simply ionic liquids - to identify their unique advantages for biocatalysis. Because they lack vapour pressure, ionic liquids hold potential as green solvents. Furthermore, unlike organic solvents of comparable polarity, they often do not inactivate enzymes, which simplifies reactions involving polar substrates such as sugars. Biocatalytic reactions in ionic liquids have also shown higher selectivity, faster rates and greater enzyme stability; however, these solvents present other challenges, among them difficulties in purifying ionic liquids and controlling water activity and pH, higher viscosity and problems with product isolation.

  1. Absorption and oxidation of nitrogen oxide in ionic liquids

    DEFF Research Database (Denmark)

    Kunov-Kruse, Andreas Jonas; Thomassen, Peter Langelund; Riisager, Anders

    2016-01-01

    . The nitric acid is absorbed in the ionic liquid up to approximately one mole HNO3 per mole of the ionic liquid due to the formation of hydrogen bonds. The nitric acid can be desorbed by heating, thereby regenerating the ionic liquid with excellent reproducibility. Here, time-resolved in-situ spectroscopic......A new strategy for capturing nitrogen oxide, NO, from the gas phase is presented. Dilute NO gas is removed from the gas phase by ionic liquids under ambient conditions. The nitrate anion of the ionic liquid catalyzes the oxidation of NO to nitric acid by atmospheric oxygen in the presence of water...

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

    Science.gov (United States)

    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.

  3. Synthetic Organic Electrochemistry in Ionic Liquids: The Viscosity Question

    Directory of Open Access Journals (Sweden)

    Scott T. Handy

    2011-07-01

    Full Text Available Ionic liquids are obvious candidates for use in electrochemical applications due to their ionic character. Nevertheless, relatively little has been done to explore their application in electrosynthesis. We have studied the Shono oxidation of arylamines and carbamates using ionic liquids as recyclable solvents and have noted that the viscosity of the medium is a major problem, although with the addition of sufficient co-solvent, good results and excellent recovery and recycling of the ionic liquid can be achieved.

  4. Antimicrobial Ionic Liquids with Fumarate Anion

    Directory of Open Access Journals (Sweden)

    Biyan He

    2013-01-01

    Full Text Available The shortage of new antimicrobial drugs and increasing resistance of microbe to antimicrobial agents have been of some concern. The formulation studies of new antibacterial and antifungal agents have been an active research field. Ionic liquids are known as designed liquids with controllable physical/chemical/biological properties and specific functions, which have been attracting considerable interest over recent years. However, no attention has been made towards the preparation of ionic liquids with antimicrobial activities. In this paper, a new class of ionic liquids (ILs with fumarate anion was synthesized by neutralization of aqueous 1-butyl-3-methylimidazolium hydroxide with equimolar monoester fumarate and characterized using NMR and thermal gravimetric analysis. The ILs are soluble in water and polar organic solvents and also soluble in the common ILs. The antimicrobial activities of the ILs are more active than commercially available potassium sorbate and are greatly affected by the alkyl chain length. The significant antimicrobial properties observed in this research suggest that the ILs may have potential applications in the modern biotechnology.

  5. [Advances of poly (ionic liquid) materials in separation science].

    Science.gov (United States)

    Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

    2015-11-01

    Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials.

  6. Supported ionic liquids fundamentals and applications

    CERN Document Server

    Fehrmann, Rasmus; Haumann, Marco

    2013-01-01

    This unique book gives a timely overview about the fundamentals and applications of supported ionic liquids in modern organic synthesis. It introduces the concept and synthesis of SILP materials and presents important applications in the field of catalysis (e.g. hydroformylation, hydrogenation, coupling reactions, fine chemical synthesis) as well as energy technology and gas separation. Written by pioneers in the field, this book is an invaluable reference book for organic chemists in academia or industry.

  7. Self-propelled chemotactic ionic liquid droplets

    OpenAIRE

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

    2015-01-01

    Herein we report the chemotactic behaviour of self-propelled droplets composed solely of the ionic liquid trihexyl(tetradecyl)phosphonium chloride ([P6,6,6,14][Cl]). These droplets spontaneously move along an aqueous-air boundary in the direction of chloride gradients to specific destinations due to asymmetric release of [P6,6,6,14]+ cationic surfactant from the droplet into the aqueous phase.

  8. INTERACTION OF IONIC LIQUIDS WITH POLYSACCHARIDES

    OpenAIRE

    2008-01-01

    The use of ionic liquids (ILs) in the field of cellulose chemistry opens up a broad variety of new opportunities. Besides the regeneration of the biopolymer to fibers, films, and beads, this new class of cellulose solvents is particularly useful for the homogeneous chemical modification of the polysaccharide. In this review, the potential of ILs as a reaction medium for the homogeneous cellulose functionalization is discussed. It is shown that numerous conversions proceed very efficiently and...

  9. Supported ionic liquids: versatile reaction and separation media

    DEFF Research Database (Denmark)

    Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco;

    2006-01-01

    The latest developments in supported ionic liquid phase (SILP) systems for catalysis and separation technology are surveyed. The SILP concept combines the advantages of homogeneous catalysis with heterogeneous process technology, and a variety of reactions have been studied where supported ionic ...... liquid catalysts proved to be more active and selective than common systems. In separation applications the use of supported ionic liquids can facilitate selective transport of substrates across membranes.......The latest developments in supported ionic liquid phase (SILP) systems for catalysis and separation technology are surveyed. The SILP concept combines the advantages of homogeneous catalysis with heterogeneous process technology, and a variety of reactions have been studied where supported ionic...

  10. Two Coexisting Liquid Phases in Switchable Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Juan; Lao, David; Sui, Xiao; Zhou, Yufan; Nune, Satish K.; Ma, Xiang; Troy, Tyler; Ahmed, Musahid; Zhu, Zihua; Heldebrant, David J.; Yu, Xiao-Ying

    2017-08-30

    In situ time-of-flight secondary ion mass spectrometry (ToF-SIMS) coupled with a vacuum compatible microfluidic reactor, System for Analysis at Liquid Vacuum Interface (SALVI), has enabled the first spatial mapping of the switchable ionic liquids (SWILs) derived from 1,8-diazabicycloundec-7-ene (DBU) and 1-hexanol. As predicted by molecular dynamic simulations, our molecular imaging results confirmed a dynamic heterogeneous molecular structure with ionic regions (high CO2 concentration) coexisting with non-ionic regions (no CO2) where stoichiometry would indicate otherwise. Chemical speciation was also found to be more complex than initially thought, with spectral principal component analysis identifying dimers that ultimately highlight a highly complex molecular structure unique to SWILs. The spatial chemical mapping enabled by ToF-SIMS and SALVI advances the understanding of how the heterogeneous molecular structure impacts the dynamic physical and thermodynamic properties or SWILs.

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

    Science.gov (United States)

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

    2013-11-15

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

  12. Periodicity and map for discovery of new ionic liquids

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    There is virtually no limit in the number of ionic liquids. How to select proper ones or discover new ones with desirable properties in such a large pool of ionic liquids? It has become a bottleneck in the researches and applications of ionic liquids. Mendeleev's periodic law states that the properties of the elements vary periodically. Whether the similar regularity exists among ionic or molecular fragments of compounds is an interesting topic. In this work, we attempted to establish a periodicity and draw a "map" of ionic liquids for providing definite guidance to discover, design, and select the proper ionic liquids rather than trial-and-error. If a complete regularity of the system of ionic liquids can be finally established in the future, we are near an epoch in understanding the existing differences and the reasons for the similarity of the ions or molecular fragments.

  13. Synthetic Organic Electrochemistry in Ionic Liquids: The Viscosity Question

    OpenAIRE

    Handy, Scott T.; Steven Bornemann

    2011-01-01

    Ionic liquids are obvious candidates for use in electrochemical applications due to their ionic character. Nevertheless, relatively little has been done to explore their application in electrosynthesis. We have studied the Shono oxidation of arylamines and carbamates using ionic liquids as recyclable solvents and have noted that the viscosity of the medium is a major problem, although with the addition of sufficient co-solvent, good results and excellent recovery and recycling of the ionic li...

  14. Application of ionic liquid in liquid phase microextraction technology.

    Science.gov (United States)

    Han, Dandan; Tang, Baokun; Lee, Yu Ri; Row, Kyung Ho

    2012-11-01

    Ionic liquids (ILs) are novel nonmolecular solvents. Their unique properties, such as high thermal stability, tunable viscosity, negligible vapor pressure, nonflammability, and good solubility for inorganic and organic compounds, make them excellent candidates as extraction media for a range of microextraction techniques. Many physical properties of ILs can be varied, and the structural design can be tuned to impart the desired functionality and enhance the analyte extraction selectivity, efficiency, and sensitivity. This paper provides an overview of the applications of ILs in liquid phase microextraction technology, such as single-drop microextraction, hollow fiber based liquid phase microextraction, and dispersive liquid-liquid microextraction. The sensitivity, linear calibration range, and detection limits for a range of target analytes in the methods were analyzed to determine the advantages of ILs in liquid phase microextraction. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ionic fluids in lubrication of aluminium-steel contacts. Surface and tribochemical interactions

    Science.gov (United States)

    Jimenez Ballesta, Ana Eva

    Room-temperature ionic liquids (ILs) are high performance fluids with a wide thermal stability range. They are being studied as new lubricants in a variety of sliding contacts. One of their more interesting tribological applications is that of steel-aluminium lubrication. In this work we study the influence of the lateral alkyl chain length and of the anion on the lubricating ability of six imidazolium ILs, a pyridinium and a phosphonium derivative. For first time, these ILs have been studied as neat lubricants and as 1wt.% base oil additives in variable conditions of velocity, load and temperature in pin-on-disk tests for AISI 52100 steel-ASTM 2011 aluminium contacts. In this work we present the first study of ILs as lubricants under extreme temperature conditions. The tribological performance of ILs has been compared with that of a mineral oil and of a synthetic ester. Under these conditions, ILs show lower friction and wear values than conventional oils at all temperatures. As 1wt.% additives, the conditions of optimum lubrication and the transitions between regimes and lubrication mechanisms have been determined. We have also studied the performance of ILs as 1wt.% additives of the synthetic oil. A relationship between additive polarity and wear index has been established. If the more soluble phosphonium IL additive is used, no friction or wear reduction takes place due to competition between solvation and adsorption processes. Electronic microscopy (SEM), energy dispersive (EDS) and X-ray photoelectron (XPS) spectroscopies have been used to study the wear mechanisms and tribochemical processes that take place in the contact. Finally, we have studied the performance of three aluminium alloys in corrosion and erosion-corrosion tests. In immersion tests with free-water ILs, the aluminium alloy 2011 shows a good resistance to corrosion, but dilution of 1-ethyl, 3-methylimidazolium tetrafluoroborate in water produces the hydrolysis of the anion and the corrosion of

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

    Science.gov (United States)

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

    2016-08-01

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

  17. Ionic Liquids in Polymer Design: From Energy to Health

    Science.gov (United States)

    2016-10-19

    SECURITY CLASSIFICATION OF: ACS Symposium: Ionic Liquids in Polymer Design: From Energy to Health at Fall 2015 ACS Meeting in Boston, MA The...combination of ionic liquids and polymers has emerged as an active field of exploration in polymer science, where new materials have be realized for...2016 Final Report: Ionic Liquids in Polymer Design: From Energy to Health The views, opinions and/or findings contained in this report are those of

  18. Basicity of pyridine and some substituted pyridines in ionic liquids.

    Science.gov (United States)

    Angelini, Guido; De Maria, Paolo; Chiappe, Cinzia; Fontana, Antonella; Pierini, Marco; Siani, Gabriella

    2010-06-04

    The equilibrium constants for ion pair formation of some pyridines have been evaluated by spectrophotometric titration with trifluoroacetic acid in different ionic liquids. The basicity order is the same in ionic liquids and in water. The substituent effect on the equilibrium constant has been discussed in terms of the Hammett equation. Pyridine basicity appears to be less sensitive to the substituent effect in ionic liquids than in water.

  19. Phase Behavior of Mixtures of Ionic Liquids and Organic Solvents

    DEFF Research Database (Denmark)

    Abildskov, Jens; Ellegaard, Martin Dela; O’Connell, J.P.

    2010-01-01

    A corresponding-states form of the generalized van der Waals equation, previously developed for mixtures of an ionic liquid and a supercritical solute, is here extended to mixtures including an ionic liquid and a solvent (water or organic). Group contributions to characteristic parameters...... solvents. Here we show results for heavier and more-than-sparingly solutes such as carbon dioxide and propane in ionic liquids....

  20. Different roles of ionic liquids in lithium batteries

    Science.gov (United States)

    Eftekhari, Ali; Liu, Yang; Chen, Pu

    2016-12-01

    Ionic liquids are often named solvents of the future because of flexibility in design. This statement has given credence that ionic liquids should simply replace the problematic electrolytes of lithium batteries. As a result, the promising potentials of ionic liquids in electrochemical systems are somehow obscured by inappropriate expectations. We summarize recent advancements in this field, especially, ionic liquids as standalone electrolytes, additives, plasticizers in gel polymer electrolytes, and binders; and attempt to shed light on the future pathway of this area of research. Ionic liquids are not dilute media to serve as pure solvents in electrochemical systems where mobility of ions is the priority; instead, they can contribute to the ionic conductivity of various components in a battery system. Owing to the enormous possibilities of ionic liquids, it is not merely a matter of choice. Ionic liquids can be used to design novel types of electrolytes for a new generation of lithium batteries. A promising possibility, which is still at a very early stage, is supercooled ionic liquid crystals for fast ion diffusion through the guided channels of a liquid-like medium. This, of course, will be a breakthrough in the realm of electrochemistry, far beyond lithium battery field, when materialized.

  1. Ionic liquid and nanoparticle hybrid systems: Emerging applications.

    Science.gov (United States)

    He, Zhiqi; Alexandridis, Paschalis

    2017-06-01

    Having novel electronic and optical properties that emanate from their nano-scale dimensions, nanoparticles are central to numerous applications. Ionic liquids can confer to nanoparticle chemical protection and physicochemical property enhancement through intermolecular interactions and can consequently improve the stability and reusability of nanoparticle for various operations. With an aim to combine the novel properties of nanoparticles and ionic liquids, different structures have been generated, based on a balance of several intermolecular interactions. Such ionic liquid and nanoparticle hybrids are showing great potential in diverse applications. In this review, we first introduce various types of ionic liquid and nanoparticle hybrids, including nanoparticle colloidal dispersions in ionic liquids, ionic liquid-grafted nanoparticles, and nanoparticle-stabilized ionic liquid-based emulsions. Such hybrid materials exhibit interesting synergisms. We then highlight representative applications of ionic liquid and nanoparticle hybrids in the catalysis, electrochemistry and separations fields. Such hybrids can attain better stability and higher efficiency under a broad range of conditions. Novel and enhanced performance can be achieved in these applications by combining desired properties of ionic liquids and of nanoparticles within an appropriate hybrid nanostructure. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Improving Stability of Gasoline by Using Ionic Liquid Catalyst

    Institute of Scientific and Technical Information of China (English)

    Gao Zhirong; Liu Daosheng; Liao Kejian; Jian Heng

    2003-01-01

    The composition, characteristics and preparation of ionic liquids are presented. The factors influencing the stability of gasoline and the significance of improving gasoline stability are discussed. A novel way to improve the stability of gasoline by using ionic liquid catalyst is developed. The contents of olefin, basic nitrogen and sulfur in gasoline are determined and the optimal experimental conditions for improving gasoline stability are established.The ionic liquid catalyst, which is environmentally friendly, can reduce the olefin content in gasoline, and such process is noted for mild reaction conditions, simple operation, short reaction time, easy recycling of the ionic liquid catalyst and ready separation of products and catalyst.

  3. Lipid extraction from microalgae using a single ionic liquid

    Science.gov (United States)

    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.

  4. ZnO-ionic liquid nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Sanes, Jose; Carrion, Francisco-Jose [Grupo de Ciencia de Materiales e Ingenieria Metalurgica, Departamento de Ingenieria de Materiales y Fabricacion, Universidad Politecnica de Cartagena, Campus de la Muralla del Mar, C/ Doctor Fleming s/n, 30202 Cartagena (Spain); Bermudez, Maria-Dolores, E-mail: mdolores.bermudez@upct.es [Grupo de Ciencia de Materiales e Ingenieria Metalurgica, Departamento de Ingenieria de Materiales y Fabricacion, Universidad Politecnica de Cartagena, Campus de la Muralla del Mar, C/ Doctor Fleming s/n, 30202 Cartagena (Spain)

    2009-02-15

    The mixture of nanostructures derived from the surface interactions and reactivity of ZnO nanoparticles with the room-temperature ionic liquid (IL1) 1-hexyl, 3-methylimidazolium hexafluorophosphate has been studied. Results are discussed on the basis of transmission electron microscopy (TEM) observations, energy dispersive spectroscopy (EDS) analysis, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) determinations. Size and morphology changes in ZnO nanoparticles by surface modification with IL1 are observed. ZnF{sub 2} crystalline needles due to reaction with the hexafluorophosphate anion are also formed.

  5. Design of Separation Processes with Ionic Liquids

    DEFF Research Database (Denmark)

    2015-01-01

    A systematic methodology for screening and designing of Ionic Liquid (IL)-based separation processes is proposed and demonstrated using several case studies of both aqueous and non-aqueous systems, for instance, ethanol + water, ethanol + hexane, benzene + hexane, and toluene + methylcyclohexane....... The best four ILs of each mixture are [mmim][dmp], [emim][bti], [emim][etso4] and [hmim][tcb], respectively. All of them were used as entrainers in the extractive distillation. A process simulation of each system was carried out and showed a lower both energy requirement and solvent usage as compared...

  6. INTERACTION OF IONIC LIQUIDS WITH POLYSACCHARIDES

    Directory of Open Access Journals (Sweden)

    Tim Liebert

    2008-05-01

    Full Text Available The use of ionic liquids (ILs in the field of cellulose chemistry opens up a broad variety of new opportunities. Besides the regeneration of the biopolymer to fibers, films, and beads, this new class of cellulose solvents is particularly useful for the homogeneous chemical modification of the polysaccharide. In this review, the potential of ILs as a reaction medium for the homogeneous cellulose functionalization is discussed. It is shown that numerous conversions proceed very efficiently and the ILs may be recycled. But it is also demonstrated that some side reactions have to be considered.

  7. Aprotic Heterocyclic Anion Triazolide Ionic Liquids - A New Class of Ionic Liquid Anion Accessed by the Huisgen Cycloaddition Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Robert [National Energy Technology Laboratory; Damodaran, Krishnan [Department of Chemistry, University of Pittsburgh; Luebke, David [National Energy Technology Laboratory; Nulwala, Hunaid [National Energy Technology Laboratory

    2013-04-18

    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.

  8. Notre Dame Geothermal Ionic Liquids Research: Ionic Liquids for Utilization of Geothermal Energy

    Energy Technology Data Exchange (ETDEWEB)

    Brennecke, Joan F. [Univ. of Notre Dame, IN (United States)

    2017-03-07

    The goal of this project was to develop ionic liquids for two geothermal energy related applications. The first goal was to design ionic liquids as high temperature heat transfer fluids. We identified appropriate compounds based on both experiments and molecular simulations. We synthesized the new ILs, and measured their thermal stability, measured storage density, viscosity, and thermal conductivity. We found that the most promising compounds for this application are aminopyridinium bis(trifluoromethylsulfonyl)imide based ILs. We also performed some measurements of thermal stability of IL mixtures and used molecular simulations to better understand the thermal conductivity of nanofluids (i.e., mixtures of ILs and nanoparticles). We found that the mixtures do not follow ideal mixture theories and that the addition of nanoparticles to ILs may well have a beneficial influence on the thermal and transport properties of IL-based heat transfer fluids. The second goal was to use ionic liquids in geothermally driven absorption refrigeration systems. We performed copious thermodynamic measurements and modeling of ionic liquid/water systems, including modeling of the absorption refrigeration systems and the resulting coefficients of performance. We explored some IL/organic solvent mixtures as candidates for this application, both with experimentation and molecular simulations. We found that the COPs of all of the IL/water systems were higher than the conventional system – LiBr/H2O. Thus, IL/water systems appear very attractive for absorption refrigeration applications.

  9. Predictive thermodynamics for ionic solids and liquids.

    Science.gov (United States)

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

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

  10. Toxicity of ionic liquids prepared from biomaterials.

    Science.gov (United States)

    Gouveia, W; Jorge, T F; Martins, S; Meireles, M; Carolino, M; Cruz, C; Almeida, T V; Araújo, 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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Cellulose multilayer Membranes manufacture with Ionic liquid

    KAUST Repository

    Livazovic, Sara

    2015-05-09

    Membrane processes are considered energy-efficient for water desalination and treatment. However most membranes are based on polymers prepared from fossil petrochemical sources. The development of multilayer membranes for nanofiltration and ultrafiltration, with thin selective layers of naturally available cellulose has been hampered by the availability of non-aggressive solvents. We propose the manufacture of cellulose membranes based on two approaches: (i) silylation, coating from solutions in tetrahydrofuran, followed by solvent evaporation and cellulose regeneration by acid treatment; (ii) casting from solution in 1-ethyl-3-methylimidazolum acetate ([C2mim]OAc), an ionic liquid, followed by phase inversion in water. By these methods porous supports could be easily coated with semi-crystalline cellulose. The membranes were hydrophilic with contact angles as low as 22.0°, molecular weight cut-off as low as 3000 g mol-1 with corresponding water permeance of 13.8 Lm−2 h−1 bar−1. Self-standing cellulose membranes were also manufactured without porous substrate, using only ionic liquid as green solvent. This membrane was insoluble in water, tetrahydrofuran, hexane, N,N-dimethylformamide, 1-methyl-2-pyrrolidinone and N,N-dimethylacetamide.

  12. Anodic dissolution of metals in ionic liquids

    Directory of Open Access Journals (Sweden)

    Andrew P. Abbott

    2015-12-01

    Full Text Available The anodic dissolution of metals is an important topic for battery design, material finishing and metal digestion. Ionic liquids are being used in all of these areas but the research on the anodic dissolution is relatively few in these media. This study investigates the behaviour of 9 metals in an ionic liquid [C4mim][Cl] and a deep eutectic solvent, Ethaline, which is a 1:2 mol ratio mixture of choline chloride and ethylene glycol. It is shown that for the majority of metals studied a quasi-passivation of the metal surface occurs, primarily due to the formation of insoluble films on the electrode surface. The behaviour of most metals is different in [C4mim][Cl] to that in Ethaline due in part to the differences in viscosity. The formation of passivating salt films can be decreased with stirring or by increasing the electrolyte temperature, thereby increasing ligand transport to the electrode surface.

  13. Advanced Ionic Liquid Monopropellant for Payload Ascent Vehicles Project

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose to develop a monopropellant replacement for hydrazine using eutectic mixtures of ionic liquids (EILs). These liquids offer us the ability to tailor fluid...

  14. Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Ogihara, Wataru; Yoshizawa, Masahiro; Ohno Hiroyuki [Tokyo University of Agriculture and Technology (Japan). Dept. of Biotechnology; Sun, Jiazeng; Forsyth, M. [Monash University, Clayton (Australia). School of Materials Engineering; MacFarlane, D.R. [Monash University, Clayton (Australia). School of Chemistry

    2004-04-30

    We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10{sup -4} to 10{sup -3} S cm{sup -1} at room temperature. Gelation was found to cause little change in the {sup 7}Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids. (author)

  15. Preparation of Ionic Liquid-based Vilsmier Reagent from Novel Multi-purpose Dimethyl Formamide-like Ionic Liquid and Its Application

    Institute of Scientific and Technical Information of China (English)

    Hullio, Ahmed Ali; Mastoi, G. M.

    2012-01-01

    In continuation of research to explore the applied potential of DMF-like ionic liquid, the ionic liquid version of N,N-dimethyliminiumchloride (Vilsmier reagent) has been synthesized from DMF-like ionic liquid and tested effectively for its capacity to achieve more useful organic transformations. The results show that DMF-like ionic liquid is world's first task specific ionic liquid which has catalyzed numerous diverse type of reaction and is multipurpose in its application. Thus a new term for this DMF-like ionic liquid has been coined that is DMF-like "multipurpose" ionic liquid.

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

    Science.gov (United States)

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

    2011-11-01

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

  17. Ionic Liquids and Green Chemistry: A Lab Experiment

    Science.gov (United States)

    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…

  18. Brownian dynamics determine universality of charge transport in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Sangoro, Joshua R [ORNL; Iacob, Ciprian [University of Leipzig; Mierzwa, Michal [University of Silesia, Uniwersytecka, Katowice, Poland; Paluch, Marian [University of Silesia, Uniwersytecka, Katowice, Poland; Kremer, Friedrich [University of Leipzig

    2012-01-01

    Broadband dielectric spectroscopy is employed to investigate charge transport in a variety of glass-forming ionic liquids over wide frequency, temperature and pressure ranges. Using a combination of Einstein, Einstein-Smoluchowski, and Langevin relations, the observed universal scaling of charge transport in ionic liquids is traced back to the dominant role of Brownian dynamics.

  19. Combined reactions and separations using ionic liquids and carbon dioxide

    NARCIS (Netherlands)

    Kroon, M.C.

    2006-01-01

    A new and general type of process for the chemical industry is presented using ionic liquids and supercritical carbon dioxide as combined reaction and separation media. In this process, the carbon dioxide pressure controls the miscibility of reactants, products, catalyst and ionic liquid, enabling f

  20. Synthesis and Characterization of Dual Acidic Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    Xiao Hua WANG; Guo Hong TAO; Zi Yan ZHANG; Yuan KOU

    2005-01-01

    Novel ionic liquids with dual acidity, of which the cation contains Bronsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR,FT-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.

  1. CO2 sorption by supported amino acid ionic liquids

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns the absorption and desorption behaviour of carbon dioxide (CO2) using ionic liquids derived from amino acids adsorbed on porous carrier materials.......The present invention concerns the absorption and desorption behaviour of carbon dioxide (CO2) using ionic liquids derived from amino acids adsorbed on porous carrier materials....

  2. Absorption and oxidation of no in ionic liquids

    DEFF Research Database (Denmark)

    2013-01-01

    The present invention concerns the absorption and in situ oxidation of nitric oxide (NO) in the presence of water and oxygen in ionic liquid compositions at ambient temperature.......The present invention concerns the absorption and in situ oxidation of nitric oxide (NO) in the presence of water and oxygen in ionic liquid compositions at ambient temperature....

  3. An Ionic Liquid Solution of Chitosan as Organocatalyst

    Directory of Open Access Journals (Sweden)

    René Wilhelm

    2013-11-01

    Full Text Available Chitosan, which is derived from the biopolymer chitin, can be readily dissolved in different ionic liquids. The resulting homogeneous solutions were applied in an asymmetric Aldol reaction. Depending on the type of ionic liquid used, high asymmetric inductions were found. The influence of different additives was also studied. The best results were obtained in [BMIM][Br] without an additive.

  4. Ionic Liquids and Green Chemistry: A Lab Experiment

    Science.gov (United States)

    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…

  5. Ionic Liquid Electrolytes for Flexible Dye-Sensitized Solar Cells

    Science.gov (United States)

    2014-09-01

    Ionic Liquid Electrolytes for Flexible Dye-Sensitized Solar Cells by Charles Brandon Sweeney, Mark Bundy, Mark Griep, and Shashi P. Karna...ARL-TR-7100 September 2014 Ionic Liquid Electrolytes for Flexible Dye-Sensitized Solar Cells Charles Brandon Sweeney Texas A&M...

  6. Multi-responsive ionic liquid emulsions stabilized by microgels

    NARCIS (Netherlands)

    Monteillet, H.J.M.; Workamp, M.J.; Li, X.; Schuur, B.; Kleijn, J.M.; Leermakers, F.A.M.; Sprakel, J.H.B.

    2014-01-01

    We present a complete toolbox to use responsive ionic liquid (IL) emulsions for extraction purposes. IL emulsions stabilized by responsive microgels are shown to allow rapid extraction and reversible breaking and re-emulsification. Moreover, by using a paramagnetic ionic liquid, droplets can be easi

  7. Soft and flexible conductive PDMS/MWCNT composites

    DEFF Research Database (Denmark)

    Hassouneh, Suzan Sager; Yu, Liyun; Skov, Anne Ladegaard;

    2017-01-01

    Conductive elastomers based on MWCNT in polydimethylsiloxane (PDMS) have been prepared by a range of dispersion methods such as ultrasonication, speedmixing and roll milling in combination with physical or covalent modification. The ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluorometh......Conductive elastomers based on MWCNT in polydimethylsiloxane (PDMS) have been prepared by a range of dispersion methods such as ultrasonication, speedmixing and roll milling in combination with physical or covalent modification. The ionic liquid (IL), 1-ethyl-3-methylimidazolium bis...... in conductivity was observed, which was attributed to a change in morphology occurring between 4 and 5 wt % MWCNT. As an alternative to IL dispersing aids a novel functionalized MWCNT was prepared by free radical polymerization using α-methacryloxypropyl-polydimethylsiloxane, which could be used directly...

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W., E-mail: ed.castner@rutgers.edu [Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854 (United States); Husson, Pascale [CNRS, UMR 6296, Institut de Chimie de Clermont-Ferrand, BP 80026, F-63171 Aubière (France); Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); Costa Gomes, Margarida F. [CNRS, UMR 6296, Institut de Chimie de Clermont-Ferrand, BP 80026, F-63171 Aubière (France); Greenbaum, Steven G. [Department of Physics and Astronomy, Hunter College, CUNY, New York, New York 10065 (United States)

    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.

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

    Science.gov (United States)

    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.

  11. Inorganic materials synthesis in ionic liquids

    Directory of Open Access Journals (Sweden)

    Christoph Janiak

    2014-01-01

    Full Text Available The field of "inorganic materials from ionic liquids" (ILs is a young and dynamically growing research area for less than 10 years. The ionothermal synthesis in ILs is often connected with the preparation of nanomaterials, the use of microwave heating and in part also ultrasound. Inorganic material synthesis in ILs allows obtaining phases which are not accessible in conventional organic or aqueous solvents or with standard methods of solid-state chemistry or under such mild conditions. Cases at hand include "ligand-free" metal nanoparticles without added stabilizing capping ligands, inorganic or inorganic-organic hybrid solid-state compounds, large polyhedral clusters and exfoliated graphene from low-temperature synthesis. There are great expectations that ILs open routes towards new, possibly unknown, inorganic materials with advantageous properties that cannot (or only with great difficulty be made via conventional processes.

  12. Energy storage materials synthesized from ionic liquids.

    Science.gov (United States)

    Gebresilassie Eshetu, Gebrekidan; Armand, Michel; Scrosati, Bruno; Passerini, Stefano

    2014-12-01

    The advent of ionic liquids (ILs) as eco-friendly and promising reaction media has opened new frontiers in the field of electrochemical energy storage. Beyond their use as electrolyte components in batteries and supercapacitors, ILs have unique properties that make them suitable as functional advanced materials, media for materials production, and components for preparing highly engineered functional products. Aiming at offering an in-depth review on the newly emerging IL-based green synthesis processes of energy storage materials, this Review provides an overview of the role of ILs in the synthesis of materials for batteries, supercapacitors, and green electrode processing. It is expected that this Review will assess the status quo of the research field and thereby stimulate new thoughts and ideas on the emerging challenges and opportunities of IL-based syntheses of energy materials.

  13. Graphene terahertz modulators by ionic liquid gating

    CERN Document Server

    Wu, Yang; Qiu, Xuepeng; Liu, Jingbo; Deorani, Praveen; Banerjee, Karan; Son, Jaesung; Chen, Yuanfu; Chia, Elbert E M; Yang, Hyunsoo

    2015-01-01

    Graphene based THz modulators are promising due to the conical band structure and high carrier mobility of graphene. Here, we tune the Fermi level of graphene via electrical gating with the help of ionic liquid to control the THz transmittance. It is found that, in the THz range, both the absorbance and reflectance of the device increase proportionately to the available density of states due to intraband transitions. Compact, stable, and repeatable THz transmittance modulation up to 93% (or 99%) for a single (or stacked) device has been demonstrated in a broad frequency range from 0.1 to 2.5 THz, with an applied voltage of only 3 V at room temperature.

  14. Polyethersulfone/Graphene Oxide Ultrafiltration Membranes from Solutions in Ionic Liquid

    KAUST Repository

    Mahalingam, Dinesh. K.

    2017-07-18

    Novel high flux polyethersulfone (PES) ultrafiltration membranes were fabricated by incorporating different amounts of graphene oxide (GO) sheets to PES as nanofillers. The membranes were prepared from solutions in 50/50 1-ethyl-3-methylimidazolium-diethylphosphate/N,N-dimethyl formamide. It was observed that the water permeance increased from 550 to 800 L m-2h-1bar-1, with incorporation of 1 wt% GO, keeping a molecular weight cut-off (MWCO) of approximately 32-34 kg mol-1. Cross-sectional scanning electron microscopy images of GO/PES membranes showed the formation of ultrathin selective layer unlike pristine membranes. Contact angle measurements confirmed the increase of hydrophilicity, by increasing the GO concentration. The rejection of humic acid and bovine serum albumin was demonstrated. The mechanical properties were improved, compared with the pristine membranes. The performance was just above the trade-off relationship between permeance and separation factor for PES membranes reported in the literature.

  15. Gas-liquid interface of room-temperature ionic liquids.

    Science.gov (United States)

    Santos, Cherry S; Baldelli, Steven

    2010-06-01

    The organization of ions at the interface of ionic liquids and the vacuum is an ideal system to test new ideas and concepts on the interfacial chemistry of electrolyte systems in the limit of no solvent medium. Whilst electrolyte systems have numerous theoretical and experimental methods used to investigate their properties, the ionic liquids are relatively new and our understanding of the interfacial properties is just beginning to be explored. In this critical review, the gas-liquid interface is reviewed, as this interface does not depend on the preparation of another medium and thus produces a natural interface. The interface has been investigated by sum frequency generation vibrational spectroscopy and ultra-high vacuum techniques. The results provide a detailed molecular-level view of the surface composition and structure. These have been complemented by theoretical studies. The combinations of treatments on this interface are starting to provide a somewhat convergent description of how the ions are organized at this neat interface (108 references).

  16. Pretreatment of Lignocellulosic Biomass with Ionic Liquids and Ionic Liquid-Based Solvent Systems

    OpenAIRE

    Qidong Hou; Meiting Ju; Weizun Li; Le Liu; Yu Chen; Qian Yang

    2017-01-01

    Pretreatment is very important for the efficient production of value-added products from lignocellulosic biomass. However, traditional pretreatment methods have several disadvantages, including low efficiency and high pollution. This article gives an overview on the applications of ionic liquids (ILs) and IL-based solvent systems in the pretreatment of lignocellulosic biomass. It is divided into three parts: the first deals with the dissolution of biomass in ILs and IL-based solvent systems; ...

  17. The rechargeable aluminum-ion battery.

    Science.gov (United States)

    Jayaprakash, N; Das, S K; Archer, L A

    2011-12-21

    We report a novel aluminium-ion rechargeable battery comprised of an electrolyte containing AlCl(3) in the ionic liquid, 1-ethyl-3-methylimidazolium chloride, and a V(2)O(5) nano-wire cathode against an aluminium metal anode. The battery delivered a discharge capacity of 305 mAh g(-1) in the first cycle and 273 mAh g(-1) after 20 cycles, with very stable electrochemical behaviour.

  18. The rechargeable aluminum-ion battery

    Energy Technology Data Exchange (ETDEWEB)

    Navaneedhakrishnan, Jayaprakash; Das, Shyamal K; Archer, Lynden A.

    2011-01-01

    We report a novel aluminium-ion rechargeable battery comprised of an electrolyte containing AlCl₃ in the ionic liquid, 1-ethyl-3-methylimidazolium chloride, and a V₂O₅ nano-wire cathode against an aluminium metal anode. The battery delivered a discharge capacity of 305 mAh g⁻¹ in the first cycle and 273 mAh g⁻¹ after 20 cycles, with very stable electrochemical behaviour.

  19. The rechargeable aluminum-ion battery

    KAUST Repository

    Jayaprakash, N.

    2011-01-01

    We report a novel aluminium-ion rechargeable battery comprised of an electrolyte containing AlCl3 in the ionic liquid, 1-ethyl-3-methylimidazolium chloride, and a V2O5 nano-wire cathode against an aluminium metal anode. The battery delivered a discharge capacity of 305 mAh g-1 in the first cycle and 273 mAh g-1 after 20 cycles, with very stable electrochemical behaviour. © The Royal Society of Chemistry 2011.

  20. Behavior of hydrophobic ionic liquids as liquid membranes on phenol removal: Experimental study and optimization

    CERN Document Server

    Ng, Y S; Hashim, M A

    2014-01-01

    Room temperature ionic liquids show potential as an alternative to conventional organic membrane solvents mainly due to their properties of low vapor pressure, low volatility and they are often stable. In the present work, the technical feasibilities of room temperature ionic liquids as bulk liquid membranes for phenol removal were investigated experimentally. Three ionic liquids with high hydrophobicity were used and their phenol removal efficiency, membrane stability and membrane loss were studied. Besides that, the effects of several parameters, namely feed phase pH, feed concentration, NaOH concentration and stirring speeds on the performance of best ionic liquid membrane were also evaluated. Lastly, an optimization study on bulk ionic liquid membrane was conducted and the maximum phenol removal efficiency was compared with the organic liquid membranes. The preliminary study shows that high phenol extraction and stripping efficiencies of 96.21% and 98.10%, respectively can be achieved by ionic liquid memb...

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

    Energy Technology Data Exchange (ETDEWEB)

    Alexia Finotello; Jason E. Bara; Dean Camper; Richard D. Noble [University of Colorado, Boulder, CO (United States). Department of Chemical and Biological Engineering

    2008-05-15

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

  2. Biophysical properties of DNA in hydrated ionic liquids

    Science.gov (United States)

    Jumbri, Khairulazhar; Ahmad, Haslina; Abdulmalek, Emilia; Rahman, Mohd Basyaruddin Abdul

    2016-11-01

    The biophysical properties and behavior of natural calf thymus DNA in hydrated 1-ethyl-3-butylimidazolium bromide ionic liquid ([C2bim]Br) have been studied using spectroscopy technique. The effect of ionic liquid concentration and temperature towards the duplex B-DNA conformation were determined. The presence of ionic liquid causes higher duplex DNA stability with the DNA melting temperature of ˜56°C without any addition of buffer solutions. The electrostatic attraction between ionic liquid's cation and DNA phosphates groups was found play a main role in stabilizing native DNA structure. Understanding of the biophysical properties of DNA in this ionic media could be used as a platform for future development of specific solvent for nucleic acid nanotechnology.

  3. Predictions of Physicochemical Properties of Ionic Liquids with DFT

    Directory of Open Access Journals (Sweden)

    Karl Karu

    2016-07-01

    Full Text Available Nowadays, density functional theory (DFT-based high-throughput computational approach is becoming more efficient and, thus, attractive for finding advanced materials for electrochemical applications. In this work, we illustrate how theoretical models, computational methods, and informatics techniques can be put together to form a simple DFT-based throughput computational workflow for predicting physicochemical properties of room-temperature ionic liquids. The developed workflow has been used for screening a set of 48 ionic pairs and for analyzing the gathered data. The predicted relative electrochemical stabilities, ionic charges and dynamic properties of the investigated ionic liquids are discussed in the light of their potential practical applications.

  4. Exfoliation of black phosphorus in ionic liquids

    Science.gov (United States)

    Lee, Miyeon; Kumer Roy, Arup; Jo, Seongho; Choi, Yujin; Chae, Ari; Kim, Bongsoo; Park, Sung Yong; In, Insik

    2017-03-01

    We report the characterization and formation of sonication-assisted liquid phase exfoliation of bulk black phosphorus (BP) crystals with the incorporation of two representative ionic liquids (ILs) ([Emim][Tf2N] and [Bmim][Tf2N]) as green dispersing media was attempted, which resulted in stable dispersion of multi-layer BP flakes with unsuspected high oxidation resistance and chemical/structural integrity due to the presence of IL layer on top of BP flakes. There are two unveiled issues for the generation of BP dispersion in ILs. First, thin films of BP flakes can be simply prepared through our approach. Because self-oxidation of BP in ambient condition can be significantly minimized in ILs, vacuum filtration step can be adopted to produce BP thin films in ambient condition. Second, the binding of IL molecules on BP flakes has been firstly demonstrated by the time-of-flight secondary ion mass spectrometry characterization. In addition to the exploitation of ILs as the green solvents with less environmental harmfulness, IL-based exfoliation of BP might be easily scalable because harsh control of atmospheric oxygen and moisture is unnecessary in this approach.

  5. Exfoliation of black phosphorus in ionic liquids.

    Science.gov (United States)

    Lee, Miyeon; Roy, Arup Kumer; Jo, Seongho; Choi, Yujin; Chae, Ari; Kim, Bongsoo; Park, Sung Yong; In, Insik

    2017-03-24

    We report the characterization and formation of sonication-assisted liquid phase exfoliation of bulk black phosphorus (BP) crystals with the incorporation of two representative ionic liquids (ILs) ([Emim][Tf2N] and [Bmim][Tf2N]) as green dispersing media was attempted, which resulted in stable dispersion of multi-layer BP flakes with unsuspected high oxidation resistance and chemical/structural integrity due to the presence of IL layer on top of BP flakes. There are two unveiled issues for the generation of BP dispersion in ILs. First, thin films of BP flakes can be simply prepared through our approach. Because self-oxidation of BP in ambient condition can be significantly minimized in ILs, vacuum filtration step can be adopted to produce BP thin films in ambient condition. Second, the binding of IL molecules on BP flakes has been firstly demonstrated by the time-of-flight secondary ion mass spectrometry characterization. In addition to the exploitation of ILs as the green solvents with less environmental harmfulness, IL-based exfoliation of BP might be easily scalable because harsh control of atmospheric oxygen and moisture is unnecessary in this approach.

  6. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    Energy Technology Data Exchange (ETDEWEB)

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center (NSRRC); 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.

  7. Soft Ionization of Thermally Evaporated Hypergolic Ionic Liquid Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Christine J. [Univ. of California, Berkeley, CA (United States); Liu, Chen-Lin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Harmon, Christopher W. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Strasser, Daniel [Univ. of California, Berkeley, CA (United States); Golan, Amir [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kostko, Oleg [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chambreau, Steven D. [Edwards Air Force Base, ERC Inc., CA (United States); Vaghjiani, Ghanshyam L. [Air Force Research Laboratory, Edwards Air Force Base, CA (United States); Leone, Stephen R. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2011-04-20

    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 submicrometer 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. Also, hotoionization 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. Lastly, the method of ionic liquid submicrometer 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.

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

    Directory of Open Access Journals (Sweden)

    Jolanta Flieger

    2015-12-01

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

  9. Soft Ionization of Thermally Evaporated Hypergolic Ionic Liquid Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Christine J. [Univ. of California, Berkeley, CA (United States); Liu, Chen-Lin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Harmon, Christopher W. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Strasser, Daniel [Univ. of California, Berkeley, CA (United States); Golan, Amir [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kostko, Oleg [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chambreau, Steven D. [Edwards Air Force Base, ERC Inc., CA (United States); Vaghjiani, Ghanshyam L. [Air Force Research Laboratory, Edwards Air Force Base, CA (United States); Leone, Stephen R. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2011-04-20

    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 submicrometer 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. Also, hotoionization 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. Lastly, the method of ionic liquid submicrometer 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.

  10. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    Energy Technology Data Exchange (ETDEWEB)

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center (NSRRC); 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.

  11. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols.

    Science.gov (United States)

    Koh, Christine J; Liu, Chen-Lin; Harmon, Christopher W; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D; Vaghjiani, Ghanshyam L; Leone, Stephen R

    2011-05-12

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim(+)][Tf(2)N(-)]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim(+)][Dca(-)]), are generated by vaporizing ionic liquid submicrometer 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(+)][Tf(2)N(-)] 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 submicrometer 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.

  12. Simultaneous Design of Ionic Liquids and Azeotropic Separation Processes

    DEFF Research Database (Denmark)

    Roughton, Brock C.; White, John; Camarda, Kyle V.;

    2011-01-01

    A methodology for the design of azeotrope separation processes using ionic liquids as entrainers is outlined. A Hildebrand solubility parameter group contribution model has been developed to screen for or design an ionic liquid entrainer that is soluble with the azeotropic components. Using...... the best candidate, vapor-liquid equilibria data is predicted using a new ionic liquid UNIFAC model that has been developed. The UNIFAC model is used to confirm the breaking of the azeotrope. The methanol-acetone azeotrope at 1 atm is used as an example. The azeotrope was predicted to break with 10 mol...... % [BMPy][BF4] added. The driving force concept is used to design an extractive distillation process that minimizes energy inputs. The methodology given can be expanded to the use of ionic liquids as entrainers in any azeotropic system of interest....

  13. Chelating ionic liquids for reversible zinc electrochemistry.

    Science.gov (United States)

    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.

  14. Periodicity and map for discovery of new ionic liquids

    Institute of Scientific and Technical Information of China (English)

    ZHANG; Suojiang

    2006-01-01

    [1]Trohalaki,S.,Pachter,R.,Drake,G.W.,Hawkins,T.,Quantitative structure-property relationships for melting points and densities of ionic liquids,Energy & Fuels,2005,19:279-284.[2]Holbery,J.D.,Seddon,K.R.,The phase behavior of 1-alkyl-3-methylimidazolium tetrafluoroborates,ionic liquids and ionic liquid crystals,J.Chem.Soc.Dalton Trans.,1999,13:2133-2139.[3]Katritzky,A.R.,Lomaka,A.,Petrukhin,R.et al.,QSPR correlation of the melting point for pyridinium bromides,potential ionic liquids,J.Chem.Inf.Comput.Sci.,2002,42:71-74.[4]Katritzky,A.R.,Jain,R.,Lomaka,A.et al.,Correlation of the melting points of potential ionic liquids (imidazolium bromides and benzimidazolium bromides) using the CODESSA program,J.Chem.Inf.Comput.Sci.,2002,42:225-231.[5]Eike,D.M.,Brennecke,J.F.,Maginn,E.J.,Predicting melting points of quaternary ammonium ionic liquids,Green Chemistry,2003,5:323-328.[6]Dupont,J.,Souza,R.F.,Suarez,A.Z.,Ionic liquid (molten salt) phase organometallic catalysis,J.Chem.Rev.,2002,102:3667-3692.[7]Turner,E.A.,Pye,C.C.,Singer,R.D.,Use of ab initio calculations toward the rational design of room temperature ionic liquids,J.Phys.Chem.A,2003,107(13):2277-2288.[8]Morrow,T.I.,Maginn,E.J.,Molecular dynamics study of the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate,J.Phys.Chem.B,2002,106:12807-12813.[9]Cadena,C.,Antony,J.L.,Shah,J.K.et al.,Why is CO2 so soluble in imidazolium-based ionic liquids? J.Am.Chem.Soc.,2004,126(16):5300-5308.[10]Liu,Z.,Huang,S.,Wang,W.,A refined force field for molecular simulation of imidazolium-based ionic liquids,J.Phys.Chem.B,2004,108(34):12978-12989.[11]Earle,M.J,Seddon,K.R.,Ionic liquids,green solvents for the future,Pure Appl.Chem.,2000,72(7):1391-1398.[12]Mendeleev on periodicity:I and II,http://www.rod.beavon.clara.net/periodic1.htm[13]Hoffmann,R.,Building bridges between inorganic and organic chemistry,Angew.Chem.Int.Ed.Engl.,1982,21(10):711-800.

  15. Spectral SAR Ecotoxicology of Ionic Liquids: The Daphnia magna Case

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz

    2007-01-01

    Full Text Available Aiming to provide a unified theory of ionic liquids ecotoxicity, the recent spectral structure activity relationship (S-SAR algorithm is employed for testing the two additive models of anionic-cationic interaction containing ionic liquid activity: the causal and the endpoint, |0+〉 and |1+〉 models, respectively. As a working system, the Daphnia magna ecotoxicity was characterized through the formulated and applied spectral chemical-ecobiological interaction principles. Specific anionic-cationic-ionic-liquid rules of interaction along the developed mechanistic hypersurface map of the main ecotoxicity paths together with the so-called resonance limitation of the standard statistical correlation analysis were revealed.

  16. Morphology-enhanced conductivity in dry ionic liquids.

    Science.gov (United States)

    Erbaş, Aykut; de la Cruz, Monica Olvera

    2016-03-01

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

  17. Utilization of Ionic Liquids for the Separation of Organic Liquids from ...

    African Journals Online (AJOL)

    NICO

    Department of Chemistry, Durban University of Technology, P.O. Box 5400, ... liquid extraction is the most widely used process for the separa- ... engineering aspect, namely, the design of a laboratory-scale ... Synthesis and Characterization of Ionic Liquids ... ionic liquids were also analyzed for BTEX content for the same.

  18. Long-range electrostatic screening in ionic liquids.

    Science.gov (United States)

    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.

  19. Morphology-induced low temperature conductivity in ionic liquids

    Science.gov (United States)

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

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

  20. Extraction of organic compounds with room temperature ionic liquids.

    Science.gov (United States)

    Poole, Colin F; Poole, Salwa K

    2010-04-16

    Room temperature ionic liquids are novel solvents with a rather specific blend of physical and solution properties that makes them of interest for applications in separation science. They are good solvents for a wide range of compounds in which they behave as polar solvents. Their physical properties of note that distinguish them from conventional organic solvents are a negligible vapor pressure, high thermal stability, and relatively high viscosity. They can form biphasic systems with water or low polarity organic solvents and gases suitable for use in liquid-liquid and gas-liquid partition systems. An analysis of partition coefficients for varied compounds in these systems allows characterization of solvent selectivity using the solvation parameter model, which together with spectroscopic studies of solvent effects on probe substances, results in a detailed picture of solvent behavior. These studies indicate that the solution properties of ionic liquids are similar to those of polar organic solvents. Practical applications of ionic liquids in sample preparation include extractive distillation, aqueous biphasic systems, liquid-liquid extraction, liquid-phase microextraction, supported liquid membrane extraction, matrix solvents for headspace analysis, and micellar extraction. The specific advantages and limitations of ionic liquids in these studies is discussed with a view to defining future uses and the need not to neglect the identification of new room temperature ionic liquids with physical and solution properties tailored to the needs of specific sample preparation techniques. The defining feature of the special nature of ionic liquids is not their solution or physical properties viewed separately but their unique combinations when taken together compared with traditional organic solvents.

  1. Separating closely resembling steroids with ionic liquids in liquid-liquid extraction systems

    NARCIS (Netherlands)

    Vitasari, C.R.; Gramblicka, M.; Gibcus, K.; Visser, T.J.; Geertman, R.M.; Schuur, B.

    2015-01-01

    Separation of steroids by liquid–liquid extraction with ionic liquids (ILs) as solvent was studied both experimentally and by simulation using a model mixture of progesterone and pregnenolone. The studies involved a solvent screening using COSMO-RS software for estimation of progesterone solubility.

  2. Synthesis of Multiester-appended and Multicarboxylic-appended Imidazolium Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    Wei Guo GENG; Xue Hui LI; Le Fu WANG; Hong Li DUAN; Wei Ping PAN

    2006-01-01

    Multiester-appended imidazolium ionic liquids were synthesized in a quatemization reaction between the imidazole derivatives carrying single or double esters and ethyl chloroacetate or bromoethane. Multicarboxylic-appended imidazolium ionic liquids were achieved from the hydrolysis of the corresponding ionic liquids. The influences of multifunctional groups on the transition temperatures and viscosity of these new ionic liquids were investigated.

  3. Enantioselective catalysis with tropos ligands in chiral ionic liquids.

    Science.gov (United States)

    Schmitkamp, Mike; Chen, Dianjun; Leitner, Walter; Klankermayer, Jürgen; Franciò, Giancarlo

    2007-10-21

    Enantioselective homogeneous rhodium-catalysed hydrogenation using tropoisomeric biphenylphosphine ligands was accomplished in readily available chiral ionic liquids and the catalytic system could be reused after extraction with scCO(2).

  4. Dissolution of cellulose in ionic liquid: A review

    Science.gov (United States)

    Mohd, N.; Draman, S. F. S.; Salleh, M. S. N.; Yusof, N. B.

    2017-02-01

    Dissolution of cellulose with ionic liquids (IL) and deep eutectic solvent (DES) lets the comprehensive dissolution of cellulose. Basically, cellulose can be dissolved, in some hydrophilic ionic liquids, such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-allyl-3-methylimidazolium chloride (AMIMCl). Chloride based ionic liquids are suitable solvents for cellulose dissolution. Although the ILs is very useful in fine chemical industry, its application in the pharmaceutical and food industry have been very limited due to issues with toxicity, purity, and high cost. Seeing to these limitations, new green alternative solvent which is DES was used. This green solvents, may be definitely treated as the next-generation reagents for more sustainable industrial development. Thus, this review aims to discuss the dissolution of cellulose either with ionic liquids or DES and its application.

  5. Non-Toxic Ionic Liquid Fuels for Exploration Applications Project

    Data.gov (United States)

    National Aeronautics and Space Administration — ORBITEC proposes to develop and test new, non-toxic ionic liquid fuels for propulsion applications. Vintage propulsion systems frequently use highly toxic...

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

    Directory of Open Access Journals (Sweden)

    Kamalakanta Behera

    2015-12-01

    Full Text Available 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.

  7. Production of biofuels and chemicals with ionic liquids

    CERN Document Server

    Fang, Zhen; Qi, Xinhua

    2013-01-01

    This book explores the application of ionic liquids to biomass for producing biofuels and chemicals. Covers pretreatment, fermentation, cellulose transformation, reaction kinetics and more, as well as subsequent production of biofuels and platform chemicals.

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

    Science.gov (United States)

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

    2015-12-04

    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.

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

    Science.gov (United States)

    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.

  10. Tunable Wavelength Soft Photoionization of Ionic Liquid Vapors (Preprint)

    Science.gov (United States)

    2009-11-18

    empirical methods to predict the physical properties of ionic liquids: An overview of recent developments. Zeitschrift Fur Physikalische Chemie...calculations. Zeitschrift Fur Physikalische Chemie- Preprint Distribution A: Approved for public release; distribution unlimited 13 International

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

    Science.gov (United States)

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

    2016-08-01

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

  12. Surface modification using ionic liquid ion beams

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-15

    We developed an ionic liquid (IL) ion source using 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF{sub 6}) 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{sup +}) or an anion (B{sup −}) was attached to an IL cluster (AB){sub n}, resulting in the formation of positive cluster ions (AB){sub n}A{sup +} or negative cluster ions (AB){sub n}B{sup −}, 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-PF{sub 6} cluster ion beams.

  13. Pretreatment of Lignocellulosic Biomass with Ionic Liquids and Ionic Liquid-Based Solvent Systems.

    Science.gov (United States)

    Hou, Qidong; Ju, Meiting; Li, Weizun; Liu, Le; Chen, Yu; Yang, Qian

    2017-03-20

    Pretreatment is very important for the efficient production of value-added products from lignocellulosic biomass. However, traditional pretreatment methods have several disadvantages, including low efficiency and high pollution. This article gives an overview on the applications of ionic liquids (ILs) and IL-based solvent systems in the pretreatment of lignocellulosic biomass. It is divided into three parts: the first deals with the dissolution of biomass in ILs and IL-based solvent systems; the second focuses on the fractionation of biomass using ILs and IL-based solvent systems as solvents; the third emphasizes the enzymatic saccharification of biomass after pretreatment with ILs and IL-based solvent systems.

  14. Cooperative nucleophilic-electrophilic organocatalysis by ionic liquids.

    Science.gov (United States)

    Lucchini, Vittorio; Noè, Marco; Selva, Maurizio; Fabris, Massimo; Perosa, Alvise

    2012-05-25

    The anionic and the cationic partners of ionic liquids may act cooperatively and independently as nucleophilic and electrophilic catalysts. This ambiphilic propensity was demonstrated by kinetically discriminating the contributions of the anion (nucleophilic catalyst) and of the cation (electrophilic catalyst) to the solvent-free Baylis-Hillman dimerization of cyclohexenone catalysed by ionic liquids. This journal is © The Royal Society of Chemistry 2012

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

    Science.gov (United States)

    Wu, Ye; Bhalla, Amar; Guo, Ruyan

    2016-03-01

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

  16. Molecular Orbital Based Design Guidelines for Hypergolic Energetic Ionic Liquids

    Science.gov (United States)

    2015-01-01

    should be synthesized to further validate our probabilistic approach for identifying EIL hypergols. DMP is one anion that has a lower “energy gap”, but...orbitals (HOMO) of the anions for a series of ionic liquids and the lowest occupied molecular orbital (LUMO) of HNO3, and variation in the computed...relative heats of formation, DHf, of these anions to develop correlations to predict hypergol activity between an ionic liquid fuel and nitric acid as

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

    Science.gov (United States)

    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.

  18. Lead-Salt Quantum-Dot Ionic Liquids

    KAUST Repository

    Sun, Liangfeng

    2010-03-08

    PbS quantum dots (QDs) are functionalized using ionic liquids with thiol moieties as capping ligands. The resulting amphiphilic QD ionic liquids exhibit fluidlike behavior at room temperature, even in the absence of solvents. The photostability of the QDs is dramatically improved compared to the as-synthesized oleic acid-capped QDs dispersed in toluene. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Development of novel ionic liquids based on biological molecules

    OpenAIRE

    Zalewska, Karolina Anna Maria

    2014-01-01

    Ionic Liquids (ILs) belong to a class of compounds with unusual properties: very low vapour pressure; high chemical and thermal stability and the ability to dissolve a wide range of substances. A new field in research is evaluating the possibility to use natural chiral biomolecules for the preparation of chiral ionic liquids (CILs). This important challenge in synthetic chemistry can open new avenues of research in order to avoid some problems related with the intrinsic biodegradability and t...

  20. First Claisen Rearrangement Reaction in Ionic Liquids with Microwave Heating

    Institute of Scientific and Technical Information of China (English)

    XU Li-Wen; LI Fu-Wei; XIA Chun-Gu

    2003-01-01

    @@ We have demonstrated the first use of the common ionic liquids, [1] bmimBr, bmimBF4 and bmimPF6 as an environmentally benign solvent for the simple Claisen rearrangement under microwave irradiation. In many cases, the re action was carried out in toxic solvents of high boiling point. [2] Here we reported the first example of Claisen rear rangement reaction in green solvents, ionic liquids, under microwave irradiation.

  1. Electrosynthesis of polyaniline in ionic liquid and its electrocatalytic properties

    Institute of Scientific and Technical Information of China (English)

    Qi Ximin; Du Yanfang; Zhang Guirong; Zhao Peng; Lu Jiaxing

    2006-01-01

    Ionic liquid like 1-butyl-3-methyl- imidazolium tetrafluorobrate ([BMIM]BF4) has been used as solvent and electrolyte for the electropolymerization of aniline at glassy carbon electrode by cyclic voltammetry.Electrode modified with polyaniline (PAn) has obvious electrochemical activity in ionic liquid and acid solution (pH 0-4),and has significant electrocatalyfic activity for redox reaction of catechol and hydroquione.

  2. Thermodynamic analysis for solubility of pimelic acid in ionic liquids

    Science.gov (United States)

    Li, Hua; Jiao, Xingli; Chen, Xiaoshuang

    2014-07-01

    Based on the solubilities of pimelic acid in ionic liquids [EMIM][HSO4], [PMIM]Br, [i-PMIM][HSO4], [BMIM]Br, and [BMIM][HSO4], dissolution enthalpy and dissolution entropy at different temperatures have been calculated. The experimental data of solubilities are correlated with the modified Apelblat equation. The thermodynamic properties of pimelic acid in ionic liquids were discussed. The solubilities correlated by the model are in good agreement with experimental data.

  3. Ionic Liquids Development and Challenges in Industrial Application

    OpenAIRE

    Cvjetko Bubalo, M.; Radošević, K.; Radojčić Redovniković, I.; Halambek, J.; Vorkapić-Furač, J.; Gaurina Srček, V.

    2014-01-01

    Establishment of novel, highly productive, and sustainable processes for the production of industrially important compounds is becoming a growing area of research. Due to non-volatility, inflammability, great thermal, chemical and electrochemical stability and also recyclability, ionic liquids are extensively studied as possible green replacement for widely used conventional molecular solvents. Due to the extremely large number of possible chemical structures of ionic liquids, the ability to ...

  4. Electrochemical Synthesis of Polythiophene in an Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry,constant potential and constant current techniques.It is found that smooth and blue-green PTh films can be obtained at a potential of ca.+1.75 V ( vs.Ag/AgCl ) or a current of ca.1.5 mA cm-2 in the ionic liquid.

  5. IONIC LIQUIDS MATERIAL AS MODERN CONTEXT OF CHEMISTRY IN SCHOOL

    Directory of Open Access Journals (Sweden)

    Hernani Hernani

    2016-04-01

    Full Text Available One way to improve students’ chemistry literacy which is demanded in the modernization of modern technology-based chemistry learning is by studying ionic liquids. Low level of scientific literacy of students in Indonesia as revealed in the PISA in 2012 was the main reason of the research. Ionic liquids-based technology are necessary to be applied as a context for learning chemistry because: (1 the attention of the scientific an technology community in the use of ionic liquids as a new generation of green solvent, electrolyte material and fluidic engineering in recent years becomes larger, in line with the strong demands of the industry for the provision of new materials that are reliable, safe, and friendly for various purposes; (2 scientific explanations related to the context of the ionic liquid contains a lot of facts, concepts, principles, laws, models and theories can be used to reinforce the learning content as a media to develop thinking skill (process/competence as demanded by PISA; (3 The modern technology-based ionic liquid can also be used as a discourse to strengthen scientific attitude. The process of synthesis of ionic liquid involves fairly simple organic reagents, so it deserves to be included in the chemistry subject in school.

  6. IONIC LIQUIDS MATERIAL AS MODERN CONTEXT OF CHEMISTRY IN SCHOOL

    Directory of Open Access Journals (Sweden)

    Hernani Hernani

    2016-04-01

    Full Text Available One way to improve students’ chemistry literacy which is demanded in the modernization of modern technology-based chemistry learning is by studying ionic liquids. Low level of scientific literacy of students in Indonesia as revealed in the PISA in 2012 was the main reason of the research. Ionic liquids-based technology are necessary to be applied as a context for learning chemistry because: (1 the attention of the scientific an technology community in the use of ionic liquids as a new generation of green solvent, electrolyte material and fluidic engineering in recent years becomes larger, in line with the strong demands of the industry for the provision of new materials that are reliable, safe, and friendly for various purposes; (2 scientific explanations related to the context of the ionic liquid contains a lot of facts, concepts, principles, laws, models and theories can be used to reinforce the learning content as a media to develop thinking skill (process/competence as demanded by PISA; (3 The modern technology-based ionic liquid can also be used as a discourse to strengthen scientific attitude. The process of synthesis of ionic liquid involves fairly simple organic reagents, so it deserves to be included in the chemistry subject in school.

  7. Ionic liquid supported acid/base-catalyzed production of biodiesel.

    Science.gov (United States)

    Lapis, Alexandre A M; de Oliveira, Luciane F; Neto, Brenno A D; Dupont, Jairton

    2008-01-01

    The transesterification (alcoholysis) reaction was successfully applied to synthesize biodiesel from vegetable oils using imidazolium-based ionic liquids under multiphase acidic and basic conditions. Under basic conditions, the combination of the ionic liquid 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMINTf2), alcohols, and K2CO3 (40 mol %) results in the production of biodiesel from soybean oil in high yields (>98%) and purity. H2SO4 immobilized in BMINTf2 efficiently promotes the transesterification reaction of soybean oil and various primary and secondary alcohols. In this multiphase process the acid is almost completely retained in the ionic liquid phase, while the biodiesel forms a separate phase. The recovered ionic liquid containing the acid could be reused at least six times without any significant loss in the biodiesel yield or selectivity. In both catalytic processes (acid and base), the reactions proceed as typical multiphasic systems in which the formed biodiesel accumulates as the upper phase and the glycerol by-product is selectively captured by the alcohol-ionic liquid-acid/base phase. Classical ionic liquids such as 1-n-butyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate are not stable under these acidic or basic conditions and decompose.

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

    Science.gov (United States)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture

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

    Science.gov (United States)

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

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

  10. Performance of Ion-gel Actuator Containing Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    H.Kokubo; Y.Kato; T.Honda; M.Watanabe

    2007-01-01

    1 Results Electroactive polymers (EAPs) driven by transducing electric energy into mechanical energy have been the subjects of recent interest[1]."Ionic liquids",consisting entirely of cation and anion,have characteristic features such as negligible volatility,non-flammability,thermal and chemical stability,and high ionic conductivity.We proposed an EAP actuator utilizing ion-gels[2-3],which consist of ionic liquids and polymers,sandwiching with two carbon material sheets as shown in Fig.1.This electrol...

  11. Spectrophotometric determination of iron species using ionic liquid ultrasound assisted dispersive liquid--liquid microextraction

    OpenAIRE

    BAZMANDEGAN, ALIREZA; Shabani,Ali Mohammad Haji; DADFARNIA, SAYESSTEH; Saeidi, Mahboubeh; Moghadam,Masoud Rohani

    2015-01-01

    A simple and efficient method for speciation and determination of iron in different water samples was developed. The method is based on ionic liquid ultrasound assisted dispersive liquid--liquid microextraction (IL-USA-DLLME) followed by spectrophotometric determination. Fe(II) is complexed with 2,4,6-tri(2'-pyridyl)-l,3,5-triazine (TPTZ{)}, neutralized through ion pair formation with sodium dodecyl sulfate (SDS) and extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate [C$_...

  12. Fast Conversion of Ionic Liquids and Poly(Ionic Liquids into Porous Nitrogen-Doped Carbons in Air

    Directory of Open Access Journals (Sweden)

    Yongjun Men

    2016-04-01

    Full Text Available Ionic liquids and poly(ionic liquids have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

  13. Ionic imbalance induced self-propulsion of liquid metals

    Science.gov (United States)

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

    2016-08-01

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