A Method for Improving Ionic Conductivity of Nafion Membranes and its Application to PEMFC

In this paper, we show that proton conductivity and PEMFC performance of Nafion membranes prepared by solutions casting can be improved by aligning the side cahin ionic aggregations along the membrane thickness direction using an electric field. The nano-structures of Nafion membranes prepared by solutions casting with applying an electric field were investigated using transmission electron microscopy (TEM), which clearly shows fibril-like structures of Nafion molecular aggregations aligned along the electric field. The alignment of ionic aggregations along the membrane thickness direction causes linear and less curved proton transferring pathways across the membrane cross section and thus a higher proton conductivity and a better PEMFC performance.     

Research Progress in Frontiers of Poly(Ionic Liquid)s: A Review

Polymeric ionic liquids or poly(ionic liquid)s combine unique properties of ionic liquids with macromolecular characteristics. One of the spotlights of review was to identify potential areas of poly(ionic liquid)s. Due to unique combination of polymer and counterions, poly(ionic liquid)s possess tunable properties to be employed in range of advanced applications. Poly(ionic liquid)s composites have claimed relevance in energy storage/production and catalysis. In biosensors, poly(ionic liquid)s were employed to fabricate enzyme electrodes. Moreover, stimuli-responsive copolymers were used to form multi-responsive poly(ionic liquid)s. Separation membranes have been reported for gas separation/storage/transport. A significant use of poly(ionic liquid)s was found as solid-state electrolyte. In fuel cell, poly(ionic liquid)s-based electrolyte membranes were employed.     

Ionic liquid/poly(ionic liquid)‐based electrolytes for energy devices

Ionic liquids are organic salts with melting points generally below 100 °C. They are attracting wide attention and are used as electrolytes in electrochemical devices, such as fuel cells, lithium‐ion batteries, dye‐sensitized solar cells, supercapacitors and light‐emitting electrochemical cells, due to their negligible vapor pressure, high ionic conductivity and wide electrochemical window. This perspective article highlights the applications of ionic liquid‐ or poly(ionic liquid)‐based electrolytes in fuel cells, dye‐sensitized solar cells and supercapacitors. © 2013 Society of Chemical Industry     

Ionic Liquid Approach Toward Manufacture and Full Recycling of All‐Cellulose Composites

All‐cellulose composites (ACCs) are prepared from high‐strength rayon fibers and cellulose pulp. The procedure comprises the use of a pulp cellulose solution in the ionic liquid (IL) 1‐ethyl‐3‐methyl imidazolium acetate ([EMIM][OAc]) as a precursor for the matrix component. High‐strength rayon fibers/fabrics are embedded in this solution of cellulose in the IL followed by removal of the IL. Different concentrations of cellulose in the IL are investigated and the mechanical properties of the final ACCs are determined via tensile, bending, and impact testing. ACCs prepared in this study show mechanical properties comparable to thermoplastic glass fiber‐reinforced plastics. Apart from being bio‐based, they possess several advantages such as biodegradability and full recyclability. The recycling of ACCs is successfully demonstrated in several cycles by using the recycled cellulose for subsequent matrix preparation.     

离子液体中氧化反应研究进展

离子液体用作氧化反应的溶剂,已经显示了许多潜在的优点。该文对在不同离子液体中进行氧化反应的类型、催化剂种类、达到的效果进行了评述,指出了存在的问题和发展方向。引用文献34篇。     

Recycling and Reuse of Ionic Liquid in Homogeneous Cellulose Acetylation

Molecular distillation was used to recover ionic liquid (IL) 1-allyl-3-methylimidazolium chloride (AmimCl) in homogeneous cellulose acetylation. The five factors that affect the separation efficiency of molecular distillation, namely, feed flow rate, distillation temperature, feed temperature, wiper rotating speed, and distillation pressure, are discussed. The optimal recovery condition was determined via orthogonal experiments using an OA₉(3⁴) design. The IL was recycled and reused 5 times in the homogeneous cellulose acetylation system under optimal conditions. The purity of recycled IL the 5th time reached 99.56%. FT-IR (Fourier transform infrared spectroscopy) and ¹H NMR (nuclear magnetic resonance) spectroscopy showed that the structure of the recovered IL is not changed. This work proves that AmimCl has excellent reusability, and that molecular distillation is an effective method for recovering IL in homogeneous cellulose acetylation.     

Thermo‐Rheology of a Proline‐Based Surface‐Active Ionic Liquid: Mixtures with Water and n‐Octane

Surfactant flooding is one of the most promising techniques to recover oil from unprofitable reservoirs. Surface‐active ionic liquids can overcome the limitations of the current surfactants. The rheology of the injecting solutions and the formed slugs is critical in the evaluation of an enhanced oil recovery process. The thermo‐rheological behavior of a biodegradable surface‐active ionic liquid, [ProC₄]DS, and the corresponding binary and ternary mixtures with water and n‐octane was studied. All flow curves exhibited shear‐thinning and thixotropic behavior. The viscoelastic behavior of the ternary samples depended strongly on the [ProC₄]DS content. Three different regions were identified: typical liquid‐like behavior, weak gel, and true gel. The thermal profiles indicated that the tested systems were fully thermoreversible.     

Key Developments in Ionic Liquid Crystals

Ionic liquid crystals are materials that combine the classes of liquid crystals and ionic liquids. The first one is based on the multi-billion-dollar flat panel display industry, whilst the latter quickly developed in the past decades into a family of highly-tunable non-volatile solvents. The combination yields materials with a unique set of properties, but also with many challenges ahead. In this review, we provide an overview of the key concepts in ionic liquid crystals, particularly from a molecular perspective. What are the important molecular parameters that determine the phase behavior? How should they be introduced into the molecules? Finally, which other tools does one have to realize specific properties in the material?     

Ionic liquid recovery alternatives in ionic liquid‐based three‐phase partitioning (ILTPP)

Ionic liquid‐based three‐phase partitioning (ILTPP) is a promising technique to recover high‐added value proteins at the liquid–liquid interface. Its economic and environmental performance highly depends on the net ionic liquid consumption. Alternatives to maximize the fraction of ionic liquid that can be recycled are studied. It is demonstrated that the addition of extra salt, previously proposed in literature, has a very limited effect on ionic liquid recovery for relatively high protein concentrations in the feed stream, and that it may even lead to an increase of the ionic liquid losses under certain conditions. However, small additions of salt are shown to be effective and profitable from an economic point of view. Vacuum evaporation is shown to allow for the complete ionic liquid and salt recovery, reinforcing the sustainability and viability of ILTPP processes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3577–3586, 2014     

硅胶固载离子液体催化剂的制备及在酯化反应中的应用

为了减少离子液体用量及解决催化剂分离问题,该文采用溶胶-凝胶法制备出一种硅胶固载Brφnsted酸性离子液体催化剂{[Hmim]TsO/silicagelw([Hmim]TsO)=62%},用DRFITS、FTRaman、BET对其进行了表征,结果表明,离子液体已较好地固载于硅胶上,催化剂比表面积为51.15m2/g。将其应用于催化合成醋酸丁酯反应,较佳反应条件为:95℃,n(丁醇)∶n(醋酸)=1.2∶1,离子液体用量为反应物总质量的5.6%,反应时间6h,酯化率可达94%。与单纯离子液体[Hmim]TsO催化效果相比,离子液体质量减少72%,酯化率提高了8.9%,催化剂易分离,循环使用6次后,酯化率仍可达到83.3%。     

Mesoscopic coarse‐grained simulations of hydrophobic charge induction chromatography (HCIC) for protein purification

Mesoscopic coarse‐grained simulations are adopted to investigate interfacial mechanisms of hydrophobic charged induction chromatography for protein purification by regulating pH. Simulations results indicate that: (i) lysozyme can be adsorbed mainly with “top end‐on” and “bottom end‐on” orientation on hydrophobic surfaces, dominated by the two hydrophobic regions located at both ends of lysozyme's long axis. Elution from the “top end‐on” orientation is more difficult than that from the “bottom end‐on” orientation; (ii) a higher ligand density can get a faster adsorption rate and stronger adsorption. Interestingly, the effect of ligand density on the desorption is mainly determined by the distribution probability of the positively charged groups of ligands; (iii) a higher ionic strength can lead to a wider orientation distribution, a stronger adsorption and a lower elution rate. This work might provide an efficient way to optimize the operating conditions and designing novel ligands. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2035–2047, 2015     

Synthesis and performance of water‐retention PEMs with nafion‐intercalating‐montmorillonite hybrid

A proton exchange membrane modified with montmorillonite (MMT) was prepared by introducing perfluorosulfonylfluroride resin into the interlayer of MMT at high temperature and high pressure. The intercalating structure was analyzed by wide‐angle X‐ray diffraction (XRD), and the results showed that the polymer was indeed intercalated into the interlayer of the modified montmorillonite (m‐MMT) matrix without destroying the microstructure of the matrix by largely increasing the d‐spacings of m‐MMT. SEM analysis on the surface and cross‐section of these composite membranes shows that the MMT nanoparticles are dispersed in the membrane uniformly. This composite membrane reveals excellent water retention and conductance at high temperature. The composite membrane was evaluated in a single cell, and the results show that the performance of composite membrane is higher than that of pure Nafion membrane at hightemperature especially without external‐humidification. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

己内酰胺苯磺酸类离子液体催化甲苯选择性硝化反应的研究

制备了己内酰胺对甲基苯磺酸和苯磺酸离子液体作为催化剂和溶剂,用于催化甲苯与等摩尔67%(m/m)硝酸的硝化反应,并用1H NMR进行了表征。研究了不同的反应温度、时间和离子液体用量及不同的离子液体等因素对甲苯硝化反应的影响。结果表明:该离子液体对甲苯的硝化有较好的对位选择性,产物中邻、对异构体质量比为1.2,较硝硫混酸硝化(邻、对异构体质量比约2.0)显著降低,收率可达37.1%,且可重复使用。     

离子液体中合成芳香磺酸酯

磺酸酯类化合物是重要的有机合成中间体,同时有着很好的药理活性。在离子液体中合成一系列标题化合物,该方法与传统的方法相比,具有反应步骤简单,条件温和,反应时间短,产率高,环境友好等优点。     

离子液体在清洁燃油中的应用研究进展

综述了离子液体在燃油脱硫工艺中的应用研究,详细介绍了离子液体在脱除直馏柴油中碱性氮化物、油品中脱酸、改进汽油安定性、在制备生物柴油中等方面的应用。对离子液体用于清洁燃料中的发展前景进行了展望。     

Performance Analysis of a HT-PEMFC System with 6FPBI Membranes Doped with Cross-Linkable Polymeric Ionic Liquid

In this paper, a high-temperature proton-exchange membrane fuel cell (HT-PEMFC) system using fluorine-containing polybenzimidazole (6FPBI) composite membranes doped with cross-linkable polymer ionic liquid (cPIL) is developed and studied. The reliability of the model is verified by a comparison with the experimental data. The performance of the HT-PEMFC system using 6FPBI membranes with different levels of cPIL is analyzed. The results show that when the HT-PEMFC uses 6FPBI membranes with a cPIL content of 20 wt % (6FPBI-cPIL 20 membranes), the single cell power density is 4952.3 W·m−2. The excessive cPIL content will lead to HT-PEMFC performance degradation. The HT-PEMFC system using the 6FPBI-cPIL 20 membranes shows a higher performance, even at higher temperatures and pressures, than the systems using 6FPBI membranes. In addition, the parametric study results suggest that the HT-PEMFC system should be operated at a higher inlet temperature and hydrogen pressure to increase system output power and efficiency. The oxygen inlet pressure should be reduced to decrease the power consumption of the ancillary equipment and improve system efficiency. The proposed model can provide a prediction for the performance of HT-PEMFC systems with the application of phosphoric-acid-doped polybenzimidazole (PA-PBI) membranes.     

离子液体在烯烃复分解反应中的应用

离子液体作为一种环境友好的催化剂和溶剂，受到了人们日益的关注。本文从离子液体作为溶剂、催化剂溶解于离子液体、离子液体的负离子作为催化剂配体三个方面，详细地介绍了离子液体在烯烃复分解反应中的应用，很好地解决了催化剂难储存、难循环利用和底物范围狭窄等问题。     

Alkylation of Ammonium Salts Catalyzed by Imidazolium‐Based Ionic Liquid Catalysts

Quaternary ammonium salts were synthesized from ammonium salts and dialkyl carbonates over imidazolium ionic liquid catalysts. The reaction gave almost stoichiometric amounts of the quaternary ammonium salts for halides and nitrates. It was found that the electron‐donating property of the alkyl moieties of ammonium cations, the electrophilic nature of the alkyl group of the carbonate, the acidity of the acid that the anion of the ammonium salt corresponds to, and the steric hindrance of the ammonium salts and the dialkyl carbonates are the key factors that influence the yields of quaternary ammonium salts. Strong electron‐donating alkyl groups on the nitrogen atom of the ammonium salt, electron‐withdrawing groups on the methylene carbon of dialkyl carbonate, and weaker steric hindrance of the starting ammonium salts and dialkyl carbonates favor the alkylation reaction of ammonium salts.     

离子液体金属电沉积研究进展

室温离子液体具有很宽的电化学窗口、优良的导电性、不挥发、热稳定性较高等优点.离子液体在化学反应、分离提纯、电化学等方面都有着广泛的应用,作为新一代绿色溶剂正日益受到重视.系统介绍了在离子液体中电化学沉积各种金属的研究进展,并展望了离子液体电沉积未来的发展趋势.