A route to heat resistant solid membranes with performances of liquid electrolytes

The confinement of ionic liquids within a porous silica matrix was performed by a one-step non-hydrolytic sol-gel route, leading to hybrid materials (called "ionogels") featuring both the mechanical and transparency properties of silica gels and the high ionic conductivity and thermal stability of ionic liquids.     

Silica-gel-confined ionic liquids: a new attempt for the development of supported nanoliquid catalysis

A new concept of designing and synthesizing highly dispersed ionic-liquid catalysts was developed through physical confinement or encapsulation of ionic liquids (with or without metal complex) in a silica-gel matrix through a sol-gel process. We studied ionic liquids such as EMImBF4, BuMImBF4, DMImBF4, CMImBF4, BuMImPF6, either with or without [Pd(PPh3)2Cl2] and [Rh(PPh3)3Cl], in a silica-gel matrix (E = ethyl, Bu = butyl M = methyl, D = decyl, C = cetyl and Im = imidazolium). The contents of ionic liquids and loadings of Pd or Rh were 8-53 wt % and 0.1 approximately 0.15 wt %, respectively. Analyses of FT-Raman spectra showed that abnormal Raman spectra of the confined ionic liquids were observed in comparison with the bulk and pure ionic liquids. EMImBF4 and BuMImBF4 ionic liquids could be completely washed out from the silica-gel matrix under vigorous reflux conditions, but ionic liquids with larger molecular size, for example, DMImBF4 or CMImBF4, could be confined into the silica-gel nanopores relatively firmly. These results suggested that the ionic liquids were physically confined or encapsulated into the silica gel. The N2 adsorption measurements indicated that the silica-gel skeleton was mesoporous with 50-110 A pore size after the BuMImBF4 ionic liquid was removed completely. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis showed that the silica-gel matrix was amorphous and non-uniformly mesoporous. Carbonylation of aniline and nitrobenzene for synthesis of diphenyl urea, carbonylation of aniline for synthesis of carbamates, and oxime transformation between cyclohexanone oxime and acetone were used as test reactions for these catalysts. Catalytic activities were remarkably enhanced with much lower amounts of ionic liquids needed with respect to bulk ionic-liquid catalysts or silica-supported ionic-liquid catalysts prepared with simple impregnation, in which the ionic liquid may be deposited as a thin layer on the support. Such unusual enhancement in catalytic activities may be attributed to the formation of nanoscale and high-concentration ionic liquids due to the confinement of the ionic liquid in silica gel; this results in unusual changes in the symmetry and coordination geometry of the ionic liquids.     

Properties of Ionic Liquid Confined in Porous Silica Matrix

Porous silica matrices of different pore sizes with confined ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) [BMIM] [PF₆] were prepared by sol‐gel technique using a tetraethyl orthosilicate (TEOS) precursor with an aim to study the changes in physico‐chemical properties of ionic liquid on confinement. It is found that on confinement 1) melting point decreases, 2) fluorescence spectra shows a red shift and 3) the vibrational bands are affected particularly those of imadazolium ring, which interacts more with the walls of the silica matrix. Preliminary theoretical calculations suggest that SiO₂ matrix interact more with the heterocyclic group of [BMIM] cation than the tail alkyl chain end group resulting in significant changes in the aromatic vibrations.     

Ionic liquid electrolytes for dye-sensitized solar cells

The potential of room-temperature molten salts (ionic liquids) as solvents for electrolytes for dye-sensitized solar cells has been investigated during the last decade. The non-volatility, good solvent properties and high electrochemical stability of ionic liquids make them attractive solvents in contrast to volatile organic solvents. Despite this, the relatively high viscosity of ionic liquids leads to mass-transport limitations. Here we review recent developments in the application of different ionic liquids as solvents or components of liquid and quasi-solid electrolytes for dye-sensitized solar cells.     

Abnormal FT-IR and FTRaman spectra of ionic liquids confined in nano-porous silica gel

A new concept of designing and synthesizing highly dispersed ionic liquids was developed through physical confinement or encapsulation of them into silica gel matrix with sol-gel process. A series of silica gel confined ionic liquids were synthesized through this process and characterized by diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) and FTRaman analysis, and abnormal FT-IR and FTRaman spectra were observed. The silica gel matrixes confined ionic liquid BMImBF(4) were further characterized by BET analysis after the ionic liquid was almost completely washed out by acetone under refluxing conditions and meso-porous silica gel matrixes were obtained according to the N(2) adsorption measurements, which suggested that the particle-size of the dispersed ionic liquids was in nano-scale. In consideration of the results obtained together, it could be found that the abnormal FT-IR and FTRaman spectra were changed with the pore-size of the silica gel matrix. For example, obvious abnormal FT-IR and FTRaman spectra appeared when the particle-size of ionic liquid BMImBF(4) is smaller than 11 nm while they disappeared again if the corresponding particle-size >11 nm. These results indicated that nano-effect, or restriction effect, produced from the nano-pores of silica gel was the reason for the abnormal FT-IR and FTRaman spectra.     

Hydrogen bonds in imidazolium ionic liquids

It is critically important to understand the structural properties of ionic liquids. In this work, the structures of cations, anions, and cation-anion ion-pairs of 1,3-dialkylimidazolium based ionic liquids were optimized systematically at the B3LYP/6-31+G level of DFT theory, and their most stable geometries were obtained. It was found that there exist only one-hydrogen-bonded ion-pairs in single-atomic anion ionic liquids such as [emim]Cl and [emim]Br, while one- and two-hydrogen-bonded ion-pairs in multiple atomic anion ionic liquids such as [emim]BF(4) and [emim]PF(6) exist. Further studies showed that the cations and anions connect each other to form a hydrogen-bonded network in 1,3-dialkylimidazolium halides, which has been proven by experimental measurement. Furthermore, the correlation of melting points and the interaction energies was discussed for both the single atomic anion and multiple atomic anion ionic liquids.     

Ionic IPNs as novel candidates for highly conductive solid polymer electrolytes

Five ionic imidazolium based monomers, namely 1‐vinyl‐3‐ethylimidazolium bis(trifluoromethylsulfonyl)imide (ILM1), 1‐vinyl‐3‐(diethoxyphosphinyl)‐propylimidazolium bis(trifluoromethylsulfonyl)imide (ILM2), 1‐[2‐(2‐methyl‐acryloyloxy)‐propyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM3), 1‐[2‐(2‐methyl‐acryloyloxy)‐undecyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM4), 1‐vinyl‐3‐ethylimidazolium dicyanamide (ILM5) were prepared and used for the synthesis of linear polymeric ionic liquids (PILs), crosslinked networks with polyethyleneglycol dimethacrylate (PEGDM) and interpenetrating polymer networks (IPNs) based on polybutadiene (PB). The ionic conductivities of IPNs prepared using an in situ strategy were found to depend on the ILM nature, T_g and the ratio of the other components. Novel ionic IPNs are characterized by increased flexibility, small swelling ability in ionic liquids (ILs) along with high conductivity and preservation of mechanical stability even in a swollen state. The maximum conductivity for a pure IPN was equal to 3.6 × 10^?5 S/cm at 20 °C while for IPN swollen in [1‐Me‐3‐Etim] (CN)₂N σ reached 8.5 × 10^?3 S/cm at 20 °C or 1.4 × 10^?2 S/cm at 50 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4245–4266, 2009     

Solvent-free aza-Markovnikov and aza-Michael additions promoted by a catalytic amount of imidazolide basic ionic liquids

A family of imidazolide ionic liquids were synthesized and characterized. These ionic liquids combined the virtues of strong basicity and relatively good thermal stability. Catalytic properties of these imidazolide ionic liquids were investigated and satisfactory yield was achieved when 2.0 mol % of [Bmim]Im was used as catalyst for aza-Markovnikov addition under solvent-free condition at room temperature in one hour. Experimental results show that a hydrogen bond is not formed between [Bmim]Im/imidazole and vinyl ester, and its existence is not necessary for the [Bmim]Im catalyzed aza-Markovnikov addition either. A possible mechanism for [Bmim]Im-catalyzed aza-Markovnikov addition was proposed. The use of imidazolide ionic liquids in aza-Michael addition was investigated as well.     

Magnetic Nanoparticles Supported Ionic Liquids Improve Firefly Luciferase Properties

Ionic liquids as neoteric solvents, microwave irradiation, and alternative energy source are becoming as a solvent for many enzymatic reactions. We recently showed that the incubation of firefly luciferase from Photinus pyralis with various ionic liquids increased the activity and stability of luciferase. Magnetic nanoparticles supported ionic liquids have been obtained by covalent bonding of ionic liquids-silane on magnetic silica nanoparticles. In the present study, the effects of [γ-Fe₂O₃@SiO₂][BMImCl] and [γ-Fe₂O₃@SiO₂][BMImI] were investigated on the structural properties and function of luciferase using circular dichroism, fluorescence spectroscopy, and bioluminescence assay. Enzyme activity and structural stability increased in the presence of magnetic nanoparticles supported ionic liquids. Furthermore, the effect of ingredients which were used was not considerable on K _m value of luciferase for adenosine-5′-triphosphate and also K _m value for luciferin.     

Cyano-containing ionic liquids for the extraction of aromatic hydrocarbons from an aromatic/aliphatic mixture

Ionic liquids can replace conventional solvents in aromatic/aliphatic extractions, if they have higher aromatic distribution coef- ficients and higher or similar aromatic/aliphatic selectivities. Also physical properties, such as density and viscosity, must be taken into account if a solvent is applied in an industrial extraction process. Cyano-containing ionic liquids have a lower den- sity than the benchmark solvent sulfolane and a higher viscosity. Sulfolane is from a hydrodynamic point of view a better sol- vent than ionic liquids for the aromatic/aliphatic extraction. The most suitable ionic liquids for the extraction of aromatic hy- drocarbons from a mixture of aromatic and aliphatic hydrocarbons are [bmim]C(CN)3, [3-mebupy]N(CN)2, [3-mebupy]C(CN)3, [3-mebupy]B(CN)4 and [mebupyrr]B(CN)4. They have factors of 1.2-2.3 higher mass-based distribution coefficients than sul- folane and a similar or higher, up to a factor of 1.9 higher, aromatic/aliphatic selectivity than sulfolane. The IL [3-mebupy]N(CN)2 is a better extractant for the separation of toluene from a mixture of toluene/n-heptane in a pilot plant Ro- tating Disc Contactor (RDC) than sulfolane.     

Recyclable 2nd generation ionic liquids as green solvents for the oxidation of alcohols with hypervalent iodine reagents

Alcohols undergo smooth oxidation with iodoxybenzoic acid (IBX) or with Dess-Martin-Periodinane (DMP) in hydrophilic [bmim]BF₄ and hydrophobic [bmim]PF₆ ionic liquids at room temperature under mild conditions to afford the corresponding carbonyl compounds in excellent yields with high selectivity. IBX and DMP promoted oxidations are faster in ionic liquids when compared to conventional solvents such as DMSO, DMF, EtOAc and H₂O. The recovery of the byproduct iodosobenzoic acid (IBA) is especially simple in ionic liquids. The recovered ionic liquids can be recycled in subsequent reactions with consistent activity.     

咪唑类离子液体用作电解质对燃料电池性能的影响

为优化改善燃料电池的整体性能,在自由电解质燃料电池中,考察了五种咪唑类离子液体用作燃料电池电解质时对燃料电池性能的影响。结果表明,以氢气为燃料时,在相同电流密度下,电路电压和输出功率从高到低依次为1-丁基-3-甲基咪唑四氟硼酸盐 > 1-丁基-3-甲基咪唑六氟磷酸盐 > 氢氧化钠溶液 >> 氯化-1-丁基-3-甲基咪唑 > 溴化-1-丁基-3-甲基咪唑 > 1-丁基-3-甲基咪唑硫酸氢盐;以甲烷为燃料时,相同电流密度下,电路电压和输出功率从高到低则依次为溴化-1-丁基-3-甲基咪唑 > 1-丁基-3-甲基咪唑硫酸氢盐 > 氯化-1-丁基-3-甲基咪唑 > 氢氧化钠溶液> 1-丁基-3-甲基咪唑四氟硼酸盐 > 1-丁基-3-甲基咪唑六氟磷酸盐。以[Bmim]BF₄为氢气燃料电池电解质时,温度升高和离子液体中水含量增加,均会使燃料电池的性能减弱。     

离子液体在多水相液液平衡体系中的作用

通过用短链离子液体(1-乙基-3-甲基咪唑溴盐[C2mim]Br、1-丁基-3-甲基咪唑溴盐[C4mim]Br)部分或全部取代SDS/DTAB/PEG/NaBr/H2O多水相体系中的无机盐NaBr,用长链离子液体十二烷基-3-甲基咪唑溴盐[C12mim]Br部分取代体系中阳离子表面活性剂DTAB,系统研究了离子液体在分相体系中的作用及其对分相体系性质的影响.研究表明,SDS/DTAB/PEG/NaBr/H2O混合体系形成的四水相体系可以看作"聚合物双水相"与"表面活性剂双水相"共存的结果.短链离子液体([C2mim]Br、[C4mim]Br)较强的亲水性能赋予其较强的盐析能力,在混合体系中表现出明显的盐效应,保证了四水相体系中"聚合物双水相"的存在.短链离子液体与聚合物之间的相互作用及其对表面活性剂之间相互作用的影响均不可忽略.对混合体系的相行为,共存多相的性质有重要的影响.而长链离子液体[C12mim]Br主要通过自身的疏水作用影响"表面活性剂双水相"的性质,充当表面活性剂的角色.然而,[C12mim]Br与DTAB分子结构上的差异,导致表面活性剂分子在"表面活性剂双水相"的两相重新分配,影响了对应两相的体积及萃取能力.可见,通过调节离子液体的烷基链长、混合体系中的含量等可获得具有特定性质的多水相体系.     

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

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) [21], [22]] 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.     

Ionic liquid/boric ester binary electrolytes with unusually high lithium transference number

Binary electrolytes composed of ionic liquids and boric esters were prepared by studying compatibility between various combinations of such systems. The study showed that out of various combinations of ionic liquids/boric esters, only TFSI anion (or FSI anion) based ionic liquids/mesityldimethoxyborane (MDMB) systems were found to be miscible. After equimolar amount of lithium salts was added to ionic liquids, the resulting solution showed high ionic conductivity that was comparable to those for ionic liquids. The lithium transference number (t_Li +) of these systems at room temperature was found to be very high. A maximum t_Li + of 0.93 was observed for a binary mixture of AMImFSI [1-allyl-3-methylimidazolium bis(fluorosulfonyl)imide]/MDMB. Further, this binary mixture as electrolyte in Li/electrolyte/Si cell showed good reversible lithiation-delithiation with > 2500 mAh/g of delithiation specific capacity.     

Investigation on solvation and protonation of meso-tetrakis(p-sulfonatophenyl)porphyrin in imidazolium-based ionic liquids by spectroscopic methods

The solvation and protonation of the meso-tetrakis(p-sulfonatophenyl)porphyrin (TPPS) were investigated by spectroscopic methods in pure or mixed imidazolium-based ionic liquids: 1-butyl-3-methyl-imidazolium terafluoroborate ([MBIM]BF₄), 1-butylimidazolium terafluoroborate ([HBIM]BF₄), 1-butyl-imidazolium dodecylalkylbenzenesulfonate ([HBIM]DS), 1-butyl-imidazolium p-toluenesulfonate ([HBIM]TS) and 1-butyl-imidazolium methylsulfonate ([HBIM]MS). Compared with absorption properties of TPPS in aqueous solution, Soret band of TPPS monomer was obviously red-shifted in the ionic liquids, while special absorption of TPPS J-aggregates was located at higher energy level, 483 nm and 702 nm, in protonic ionic liquids (PILs) [HBIM]BF₄. Next, the protonation of TPPS in aprotonic ionic liquids (AILs, i.e., [MBIM]BF₄) is dependent not only on the concentration of protonic ionic liquids as proton sources, but also on the characteristic of anion and viscosity of PILs. The proton transfer constants between TPPS and four protonic ionic liquids are (2.32 ± 0.23) × 10² for [HBIM]BF₄, (1.52 ± 0.08) × 10² for [HBIM]MS, (1.12 ± 0.21) × 10² for [HBIM]DS and (0.84 ± 0.45) × 10² for [HBIM]TS, respectively.     

Supported absorption of CO2 by tetrabutylphosphonium amino acid ionic liquids

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

Comparison of physicochemical properties of new ionic liquids based on imidazolium, quaternary ammonium, and guanidinium cations

More than 50 ionic liquids were prepared by using imidazolium, quaternary ammonium, and guanidinium cations and various anions. In these series, different cationic structures such as 1-benzyl-3-methylimidazolium [Bzmim]+, 1,3-dibenzylimidazolium [BzmiBz]+, 1-octyl-3-methylimidazolium [C8mim]+, 1-decyl-3-methylimidazolium [C10mim]+, tricapryl-methylammonium [Aliquat]+, benzyltriethylammonium [BzTEA]+, phenyltrimethylammonium [PhTMA]+, and dimethyldihexylguanidinium [DMG]+ were combined with anions, p-toluenesulfonate [TSA](-), dicyanoamide [DCA]-, saccharine (2-sulfobenzoic acid imide sodium salt) [SAC]-, trifluoroacetate [TFA]-, bis(trifluoromethanesulfonyl)imide [Tf2N]-, trifluoromethanesulfonate [TfO]-, and thiocyanate [SCN]-. Important physical data for these ionic liquids are collated, namely solubility in common solvents, viscosity, density, melting point and water content. Apart from the viscosity, the Newtonian and non-Newtonian behavior of these ionic liquids is also disclosed. Stability of these ionic liquids under thermal, basic, acidic, nucleophilic, and oxidative conditions was also studied. The features of the solid-liquid phase transition were analyzed, namely the glass transition temperature and the heat capacity jump associated with the transition from the non-equilibrium glass to the metastable supercooled liquid. A degradation temperature of each ionic liquid was also determined. Comparisons of the properties of various ionic liquids were made.     

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.     

Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

Polymer electrolytes containing N,N′-(trans-cyclohexane-1,4-diyl)dibenzamide linkages, polyethylene ((CH₂)_m, m = 2, 4, 10) spacers, and bis(trifluoromethanesulfonyl)amide (TFSA) or bis(fluorosulfonyl)amide (FSA) counteranions (polymer abbreviation: CDBAm•X; m = 2, 4, 10; X = TFSA, FSA) have been synthesized, adding to our previous report (m = 6). In addition, their ability to effect the gelation of six ionic liquids and the properties of the resulting ionogels have been examined. The polymers, except for CDBA10•TFSA, effect the gelation for all ionic liquids used in this study at fairly low concentrations (0.9–50 g/L). Ionogel ionic conductivity is not dependent on the spacer length, but does decrease slightly as increasing amounts of the gelatinizer are introduced. In contrast to ionic conductivity, the temperatures at which these ionogels transition into isotropic fluids is dependent on the spacer length; the gel composed of [EMI][FSA] and 100 g/L of CDBA6•FSA transforms at 120 °C, while the gel composed of [EMI][FSA] and 5 g/L of CDBA2•FSA does not transform into a sol even when temperatures become 155 °C. In brief, ionogel heat resistance can be improved by changing the spacer length of the polyelectrolyte. Finally, it has been determined using cyclic voltammetry that the potential window of the polyelectrolytes is particularly wide, ranging from −1.6 to 2.5 V. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 249–255