Geometric Matching Principle for Adsorption Selectivity of Ionic Liquids: A Simple Method into the Fascinating World of Shape‐Controlled Chemistry

Ionic liquids (ILs) possess effective functions in controlling the phase and morphology of nanomaterials. However, it is still unclear how ILs affect the morphology control and what the origin of adsorption selectivity of ILs is on different crystal facets. It is a challenge to develop a simple method to select the suitable kinds of ILs for achieving the controllable synthesis of nanomaterials with designable shape. Herein, density functional theory (DFT) calculations were combined with experiment to study the interaction mechanism between ILs and crystal facets. An important relationship is proposed, named as the geometric matching principle, in which the adsorption site of substrate should not only need to meet the space requirement for interionic stacking of ILs, but also needs to maximize the interaction between adsorbed ILs and substrate. This new finding is meaningful for prediction of the adsorption selectivity of ILs and clarification of their shape‐controlled chemistry.     

Evaluation of Spectroscopic and Morphological Properties of PMMA Modified with ILs

Summary: In recent years, an important class of new compounds, ionic liquids (ILs), has been investigated as additives for polymers. In this work, we carried out the synthesis of 4 different ILs: 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM.BF₄), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM.PF₆), and the chiral ILs acetyl-(−)menthol-1-buthylimidazole tetrafluoroborate ([amebim]BF₄) and acetyl-(−)menthol-1-buthylimidazole hexafluorophosphate ([amebim]PF₆). These ILs were added to poly(methyl methacrylate) (PMMA) in 10, 20 and 30% ratios by weight and the ILs, PMMA and the obtained materials (PMMA:ILs) were characterized by infrared, visible spectroscopy and atomic force microscope. The ILs added to PMMA did not provide significant changes in the infrared spectra, compared to pure PMMA. However, the absorption spectra in the visible region of the PMMA:ILs materials showed differences, compared to the spectrum of pure PMMA.     

离子液体催化CO2与环氧化物合成环状碳酸酯

综述了离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展。目前报道的离子液体主要包括咪唑盐、季铵盐、季鏻盐等。对比了传统离子液体与功能化离子液体对CO2环加成反应的催化活性、选择性以及催化作用机制。与传统的离子液体相比,功能化离子液体的羟基或羧基等官能团与卤素离子等Lewis碱之间存在协同效应,使得其对CO2与环氧化物的环加成反应具有更好的催化活性;将功能化离子液体固载于无机材料(SiO2,SBA-15,MCM-41等)或聚合物所得的多相催化剂不仅保持了官能团与阴离子之间的协同效应,而且载体与离子液体活性组分之间也显示出协同效应,使得该类催化剂具有很好的催化活性,稳定性好,可以多次重复使用,具有较好的工业化前景,是值得深入研发的一类催化材料。此外,离子液体对于手性环状碳酸酯的合成也具有较好的催化活性和立体选择性。     

Electrochemical Quantification of Hygroscopicity of Ionic Liquids with Solution‐Dissolved Potassium Ferricyanide as the Redox Probe

Quantification of hygroscopicity of ionic liquids (ILs) is of great importance in both fundamental studies and practical applications of ILs. This study demonstrates an electrochemical method for effectively quantifying the hygroscopicity of ILs through electrochemically monitoring water contents absorbed into ILs. The measurements of water content absorbed into the ILs are performed with square wave voltammetry (SWV) based on the water‐induced enhancement of diffusion of solution‐dissolved potassium ferricyanide (K₃Fe(CN)₆) redox probe. For demonstration, two kinds of ILs with different hygroscopicity (i.e., hydrophilic Bmim⁺Gly^? and hydrophobic Bmim⁺PF₆^?) are employed in this study. The dissolution of K₃Fe(CN)₆ redox probe into ILs is found to have little effect on the hygroscopicity of ILs. The hygroscopicity of ILs is thus able to be quantified by monitoring water content absorbed into ILs as a function of time when ILs are stored at room temperature and standard atmospheric pressure under 55 % relative humidity (RH). Under the conditions employed in this study, the hygroscopicity of Bmim⁺Gly^? and Bmim⁺PF₆^? is determined to be 1.33 M per hour and 0.05 M per hour, respectively, which are almost consistent with those measured with Karl Fischer titration under the same conditions. The electrochemical method demonstrated in this study is experimentally simply and environmentally benign and may be potentially extended for general quantification of hygroscopicity of ILs.     

Electrodeposition in Ionic Liquids

Due to their attractive physico‐chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template‐assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air‐ and water‐stable ILs, deep eutectic solvents (DESs), ILs with metal‐containing cations, and protic ILs. Template‐assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted.     

Basic ionic liquids promoted chemical transformation of CO_2 to organic carbonates

Ionic liquids(ILs), especially basic ILs with unique physicochemical properties, have wide application in catalysis. Using basic ILs as catalysts for the conversion of cheap, abundant, nontoxic, and renewable CO_2 into value-added organic carbonates is highly significant in view of environmental and economic issues. This review aims at giving a detailed overview on the recent advances on basic ILs promoted chemical transformation of CO_2 to cyclic and linear carbonates. The structures of various basic ILs, as well as the basic ILs promoted reactions for the transformation of CO_2 to organic carbonates are discussed in detail,including the reaction conditions, the yields of target products, the catalytic activities of basic ILs and the reaction mechanism.     

Static dielectric constant of room temperature ionic liquids: internal pressure and cohesive energy density approach

Measurements of the static dielectric constant (epsilon) of ionic liquids (ILs) are very difficult because of the decay of field by the ionic conductivity of ILs. Herein, we describe an easy method for the prediction of epsilon of various imidazolium-based ILs [C_n mim] from n, i.e. the ratio of internal pressure (P_i) and cohesive energy density (ced). A calibration curve of n vs epsilon for conventional organic solvents (mainly the linear alcohols) has been used to estimate the epsilon of the ILs. Estimated epsilon values for ILs having the anions [Cl]-, [BF 4]-, [PF 6]-, [TfO]-, and [Tf 2N]- showed a very good comparison with the literature results, whereas ILs having the anions [C_n OSO3]- tend to deviate from such correlation. Also, for a series of ILs having a common anion, the epsilon is shown to follow a very good correlation with the molecular volumes. Predicted values show that both the nature of the anion and alkyl chain length of the cation contribute significantly to the epsilon of the ILs. The method developed makes use of properties which can be either experimentally determined or estimated with good accuracy and can be extended to the other categories of ILs with ease and reasonable accuracy.     

离子液体对木瓜蛋白酶催化特性的影响

研究了以1-丁基-3-甲基咪唑、四乙基铵及N-乙基吡啶为阳离子, 配以多种阴离子(H₂PO₄^-, ClO₄^-, HSO₄^-, CH₃COO^-, Cl^-, Br^-, NO₃^-, SCN^-, BF₄^-, PF₆^-)的离子液体对木瓜蛋白酶催化N-苯甲酰-L-精氨酸乙酯(BAEE)水解的活性及热稳定性的影响. 通过分析含离子液体体系中木瓜蛋白酶的水解活性和热力学失活参数, 发现该酶活性及稳定性与离子液体的Kosmotropicity性质无关. 因此, 离子的Hofmeister效应并不适合解释离子液体对木瓜蛋白酶催化特性的影响规律. 当以BF₄^-为阴离子, 改变阳离子结构时, 仅[BMIm][BF₄]可提高酶活性, 其它含官能团的咪唑类离子液体则降低酶活性, 但大部分离子液体明显提高木瓜蛋白酶的热稳定性. 在所研究的离子液体中, 基于PF₆^-或BF₄^-阴离子的离子液体可提高木瓜蛋白酶的活性及其热稳定性. 在含[BMIm][PF₆]介质中, 木瓜蛋白酶的水解活性最高; 在含[HOEtMIm][BF₄]介质中其热稳定性最好.     

Experimental vapor pressures of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides and a correlation scheme for estimation of vaporization enthalpies of ionic liquids

Vapor pressures for a series of 1-n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (alkyl = ethyl, butyl, hexyl, and octyl) ionic liquids (ILs) were measured by the integral effusion Knudsen method. Thermodynamic parameters of vaporization for ILs were calculated from these data. The absence of decomposition of ILs during the vaporization process was proved by IR spectroscopy. Enthalpies of vaporization of ILs were correlated with molar volumes and surface tensions of the compounds.     

Binding Gibbs energy of ionic liquids to calf thymus DNA: a fluorescence spectroscopy study

The binding constants and binding Gibbs energies of [C(n)mim]Br (n = 4, 6, 8, 10, 12) and [C(4)mim][BF(4)] to calf thymus DNA-D1501 have been determined by the fluorescence measurements of the pyrene probe. It was found that values of the binding Gibbs energy decrease linearly with the increase of alkyl chain length of the ILs. Based on this observation, Gibbs energies for both the interaction between DNA and -CH(2)- of the ILs and the interaction between DNA and the cationic head group of the ILs have been reported. The result suggests that electrostatic interaction between DNA and the cationic head group of the ILs is predominant for the binding of the ILs with DNA although contribution from the non-electrostatic interaction between DNA and the alkyl chain of the ILs increases with increasing alkyl chain length of the ILs. The information obtained here may have application in the design of novel ILs-based DNA extraction/separation systems.     

离子液体在乙烯/乙烷和乙烯/乙炔分离中的应用

乙烯,作为石油化工行业的龙头原料,其高效回收分离具有重要的战略意义。离子液体作为一种结构可调控的新型绿色溶剂,在乙烯的回收分离中展现出巨大的应用前景。本文总结了近年来离子液体在乙烯/乙烷和乙烯/乙炔分离方面的研究进展,从溶剂吸收、膜吸收和与多孔材料相结合的吸附分离法等角度展开,系统地阐述了常规离子液体、功能化离子液体、聚离子液体等纯组分体系及多组分体系在不同分离方法中的研究现状,展望了离子液体在乙烯回收分离方面的应用前景和发展趋势。     

Formation and tribological properties of two‐component ultrathin ionic liquid films on Si

Several single‐component and two‐component imidazolium ionic liquids (ILs) ultrathin films were formed on Si substrates by a dip‐coating and heat treatment process. The formation and surface properties of the films were analyzed by means of ellipsometric thickness measurement, X‐ray photoelectron spectra and atomic force microscope. The adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball‐on‐plate tribometer was used to test the microtribological performances of these films. As a result, the two‐component ILs ultrathin film containing 80% solid‐like ILs phase shows more homogenous surface morphologies and optimal micro/nano‐tribological properties as compared to single‐component ILs films, which is ascribed to a synergic effect between the steady solid‐like ILs phase as the backbone and the proper amount of flowable liquid‐like ILs phase. By studying the influence of various solid/liquid ILs ratios on tribological properties of the two‐component ILs films, we might find the way to design ILs films with excellent comprehensive tribological properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?

The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs (including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.     

Effects of Ionic Liquids on Metalloproteins

In the past decade, innovative protein therapies and bio-similar industries have grown rapidly. Additionally, ionic liquids (ILs) have been an area of great interest and rapid development in industrial processes over a similar timeline. Therefore, there is a pressing need to understand the structure and function of proteins in novel environments with ILs. Understanding the short-term and long-term stability of protein molecules in IL formulations will be key to using ILs for protein technologies. Similarly, ILs have been investigated as part of therapeutic delivery systems and implicated in numerous studies in which ILs impact the activity and/or stability of protein molecules. Notably, many of the proteins used in industrial applications are involved in redox chemistry, and thus often contain metal ions or metal-associated cofactors. In this review article, we focus on the current understanding of protein structure-function relationship in the presence of ILs, specifically focusing on the effect of ILs on metal containing proteins.     

Influence of Substituents and Functional Groups on the Surface Composition of Ionic Liquids

We have performed a systematic study addressing the surface behavior of a variety of functionalized and non‐functionalized ionic liquids (ILs). From angle‐resolved X‐ray photoelectron spectroscopy, detailed conclusions on the surface enrichment of the functional groups and the molecular orientation of the cations and anions is derived. The systems include imidazolium‐based ILs methylated at the C2 position, a phenyl‐functionalized IL, an alkoxysilane‐functionalized IL, halo‐functionalized ILs, thioether‐functionalized ILs, and amine‐functionalized ILs. The results are compared with the results for corresponding non‐functionalized ILs where available. Generally, enrichment of the functional group at the surface is only observed for systems that have very weak interaction between the functional group and the ionic head groups.     

Basic ionic liquids promoted chemical transformation of CO<Subscript>2</Subscript> to organic carbonates

Ionic liquids (ILs), especially basic ILs with unique physicochemical properties, have wide application in catalysis. Using basic ILs as catalysts for the conversion of cheap, abundant, nontoxic, and renewable CO₂ into value-added organic carbonates is highly significant in view of environmental and economic issues. This review aims at giving a detailed overview on the recent advances on basic ILs promoted chemical transformation of CO₂ to cyclic and linear carbonates. The structures of various basic ILs, as well as the basic ILs promoted reactions for the transformation of CO₂ to organic carbonates are discussed in detail, including the reaction conditions, the yields of target products, the catalytic activities of basic ILs and the reaction mechanism.     

Brønsted acidic ionic liquids as dual catalyst and solvent for environmentally friendly synthesis of chalcone

Brønsted acidic ionic liquids (ILs) as dual catalyst and solvent offer a potential substitute for conventional homogenous/heterogeneous catalysts and solvent for Claisen–Schmidt (CS) condensation between acetophenone and benzaldehyde to produce chalcones. The ILs showed good catalytic activities and recycle capabilities. Both the structure of cation and anion of ILs could affect the activity of ILs. The optimized reaction conditions were investigated.     

Novel synthesis of high‐molecular‐weight prepolymer of poly(p‐phenylene benzoxazole) in ionic liquids

Using ionic liquids (ILs) as the reaction solvent for the synthesis of prepolymer polyamide of poly(p‐phenylene benzoxazole) (PBO) was investigated. The optimum condition of prepolymer preparation was determined in ILs. A series of 1,3‐dialkylimidazolium ILs were used to be the reaction media of the polycondensation. The relationship between the molecular weight of prepolymer and the structure of ILs was analysed by changing the structure of the cation and species of anion of ILs. In order to prove the feasibility of the transformation, the prepolymer was used to prepare PBO in polyphosphoric acid media, and the conversion process was analyzed. The spinnability of the PBO solution was explored by the preparation of PBO fibers. The basic mechanical properties of PBO single fiber were tested. In a word, using 1,3‐dialkylimidazolium ILs as the reaction solvents was feasible for the synthesis of high‐molecular‐weight PBO prepolymer, which could be a promising PBO preparation method.     

石英晶体微天平技术研究咪唑类离子液体与气体分子的相互作用

基于石英晶体微天平(Quartz Crystal Microbalance, QCM)技术, 建立了一种测定气体在离子液体(ILs)中基本热力学参数的方法. 测定了5种可挥发有机物(VOCs)在6种咪唑类离子液体中的亨利常数, 并对可能的作用机理进行了探讨. 结果表明, QCM技术可以作为研究离子液体溶解性和作用规律的有效方法.     

The molecular characteristics dominating the solubility of gases in ionic liquids

This critical review provides a critical discussion of the current state of knowledge of the key factors influencing the solubility of gases in ionic liquids (ILs), including sample purity, experimental methodology, "molecular" characteristics of ILs, temperature and pressure. The review starts with a brief introduction to the current developments and the existing problems in the studies of the gas solubility in ILs. Then, the experimental, computational and theoretical developments in conformational equilibria of ions, in nanosegregated polar and nonpolar domains in ILs, and in the mechanisms for dissolution of gases in ILs are discussed and subsequently collaborated together with our freeze-fracture transmission electron microscopic and Raman measurements to propose the new microscopic mechanism for dissolving the gases in ILs. Next, a critical and quantitative analysis of the influences of the sample purity and the experimental methodology on the gas solubility is made so that the "real" relationships between structure and solubility property can be revealed. In addition, a systematic and deeper understanding of how the "molecular" features of the ILs, the temperature, and the pressure influence the gas solubility is provided at the molecular level. In the section of concluding remarks, the comments are made on the molecular criteria for the future design of the ILs to enhance the gas solubility by specifically optimizing the molecular characteristics of the ILs (265 references).