二元混合离子液体的电导率与离子间的缔合作用

在293.15-323.15 K范围内, 测定了13种常见离子液体及其25组混合体系的电导率. 利用Vogel-Tammann-Fulcher (VTF)方程对电导率数据进行拟合, 并通过方程式中的拟合参数分析了离子液体混合后其阴阳离子间缔合作用的变化规律. 结果表明,在相同温度下, 离子液体的阳离子侧链越短,阴离子电荷越分散, 阴阳离子间的氢键作用力越弱,离子液体的电导率越大, 其中阴离子的影响比阳离子更明显.混合离子液体中离子间的缔合作用不仅与阴阳离子的种类有关,而且与混合物的组成有关.     

聚离子液体的合成及应用

聚离子液体(PILs)是在重复单元上具有阴、阳离子电解质基团的聚合物。此类聚合物结合了离子液体和聚合物的一些性质,近年来在高分子化学和材料科学等领域受到广泛关注。本文将聚离子液体划分为聚阳离子型离子液体、聚阴离子型离子液体、聚两性型离子液体和共聚型离子液体四类并介绍了聚离子液体的性质及各类聚离子液体的合成。此外,本文还对聚离子液体在有机分散剂、纳米复合材料、电化学、吸附剂和分离等方面的应用进行了综述。     

离子液体捕集CO2

CO₂是导致温室效应的最主要成分,因此碳捕集技术的研究受到学术界和产业界的高度重视。离子液体具有不挥发、不燃烧、热稳定性好、溶解能力强、结构和性质可调节并可循环使用等特性,在CO₂的吸收/分离领域展现了广阔的应用前景。本文系统地综述了近年来常规离子液体、功能化离子液体、支撑离子液体膜、聚合离子液体以及离子液体与分子溶剂的混合物在捕集CO₂方面的研究进展;讨论了离子液体的阳离子结构、阴离子类型、烷基链长度、阴/阳离子的氟化程度和功能化、离子液体的负载作用和聚合效应以及体系的温度和压力对CO₂选择性捕集性能的影响;分析了可能的捕集机理以及各种捕集方法的优点和缺点;提出了目前需要进一步研究的若干重要问题,并对其发展前景进行了展望。     

核磁共振波谱技术在室温离子液体研究中的应用*

室温离子液体作为一种绿色溶剂和功能材料,越来越引起人们的重视,其研究手段也越来越多。本文着重概述了核磁共振方法在测定离子液体的结构、纯度及性质,研究离子液体阴阳离子间的相互作用、离子液体与其他化合物的相互作用、离子液体及其在混合体系中的动力学特征、离子液体在溶液中的聚集行为,以及测定离子液体的热力学参数中的应用。     

含能盐和含能离子液体

近年来含能盐和含能离子液体由于其独特的性质而受到广泛关注。本文综述了多种含能盐和含能离子液体（阳离子包括三唑、四唑、双环唑、六次甲基四胺等;阴离子包括硝酸根、高氯酸根、硝基唑、叠氮根、四硝基铝、多腈基化合物、二硝基尿素等）的合成;结合其表征结果分析了阳离子上的取代基以及阴阳离子对它们的性能如熔点、生成焓、密度等的影响。对含能盐和含能离子液体在炸药和推进剂方面的应用进行了展望。     

含氟离子液体的研究进展

近年来人们对离子液体的兴趣不断增长。室温离子液体是一类熔点在室温附近的熔融盐,以其显著的特性在电化学、有机合成、催化、分离等领域被广泛应用。离子液体与氟化学紧密相关,离子液体中含有多种氟阴离子的烷基铵盐、咪唑盐等的合成、性质以及应用已经得到研究。离子液体的阴阳离子中氟原子数量和位置的不同,使离子液体具有不同的性质,如耐水性、耐温性、粘度、密度、表面张力、液体范围、导电性等。含氟的离子液体是离子液体的主要品种,它们凭借良好的可设计性和绿色环保的特点在当今化工工程的绿色化进程中显示出巨大的潜力和广阔的应用前景。     

离子液体的周期性变化规律及导向图

离子液体是完全由阴阳离子组成的室温下呈液态的盐类, 其作为绿色溶剂近年来成为众多领域的研究热点. 由于阴阳离子种类繁多, 阴阳离子的不同组合而形成的离子液体种类理论上几乎是无限的. 而在庞大的离子液体家族中如何选择合适的离子液体或者如何设计新型的功能离子液体成为离子液体研究及其应用的瓶颈. 门捷列夫的元素周期律启发我们在离子液体中寻找与之类似的规律. 本文正是基于这样一个思路, 试图建立离子液体周期率和离子液体导向图, 从而为寻找和设计离子液体提供明确的方向. 如果最终能够建立起一套完整的离子液体各种性质的周期律, 将会从本质上理解离子间及分子片间的性质差异与相互作用.     

[EPy]Cl和[EPy]Br离子对的气相和液相结构及阴阳离子间的相互作用

采用密度泛函理论B3LYP/6-31+G(d,p)方法对氯化乙基吡啶([EPy]Cl)、溴化乙基吡啶([EPy]Br)的离子对进行了结构优化和频率分析, 并利用自洽反应场(SCRF)的导体极化连续模型(CPCM)考察了离子液体液相下的结构及相互作用. 得到了两种离子液体的离子对在气相、液相下最稳定结构及气相红外光谱特征值, 两种离子液体的离子对结构存在相似性, 红外光谱特征值与文献值比较吻合. 应用自然键轨道(NBO)理论分析了离子对中原子电荷分布及电荷转移情况, 结果证明两种离子液体中阴阳离子间除了静电相互作用外还存在着氢键作用. 通过对比气相及液相下的几何参数、相互作用能及NBO分析结果, 发现液相下阴阳离子的相互作用明显降低. 液相环境抵消了大部分阴阳离子间的静电作用, 导致液相下阴阳离子间相互作用的减小.     

不同离子液体中三氯化铁的电化学行为

本文采用循环伏安法研究了FeCl3在五种不同的离子液体(包括疏水性和亲水性的离子液体)中的电化学行为,计算了不同离子液体中FeCl4的扩散系数.实验结果表明:Fe3+在离子液体中的氧化还原过程是一个具有较高可逆性的扩散控制过程.离子液体的阴、阳离子的结构及大小对Fe3+的电化学响应有影响,且离子液体的阴离子的影响较阳离子更大一些.     

N-羧基吡啶功能化离子液体的表征

合成了系列新型N-羧基吡啶功能化离子液体, 利用1H NMR、13C NMR、IR、DSC对其进行表征并研究了其与常规溶剂的相溶性, 采用酸碱滴定法测量了系列离子液体的酸离解常数pKa值. N-羧基取代吡啶功能化离子液体的pKa值在2.5~4.0之间, 并随阳离子取代羧基碳链的增长而增大; 离子之间形成氢键及阴、阳离子的大小是影响离子液体熔点的主要因素. 阴离子越小, 熔点越高. 所合成的N-羧基吡啶功能化离子液体具有相同的相溶性且由取代羧基所决定, 与常见烷基咪唑离子液体相比, N-羧基吡啶功能化离子液体与丙酮、二氯甲烷并不相溶. 功能化离子液体的阳离子取代基是影响其物化性能的主要因素, 通过改变功能化基团碳链的长短及与不同阴离子进行组合, 可以对功能化离子液体物理、化学性能进行调节.     

色谱分析中离子液体的应用及其测定

离子液体作为一种优良的溶剂越来越受到人们的关注。由于离子液体特殊的物理化学性质使其在色谱分析中也得到了较广泛的应用。本文综述了离子液体在气相色谱、高效液相色谱和毛细管电泳中的应用,其中包括离子液体作为气相色谱的固定相、高效液相色谱的固定相及流动相添加剂和毛细管电泳的电解质添加剂等,并对离子液体的色谱分离检测作了详细介绍。     

室温离子液体在分离分析中的应用

室温离子液体是指室温或接近室温下全部由离子组成的有机液体物质,具有不挥发,不易燃,溶解范围大,对空气和热稳定等特点,作为一种“可设计”型的环境相对友好溶剂,已被成功应用于分离分析领域中。本文重点综述了离子液体近年来在毛细管电泳、液相色谱及气相色谱中的应用进展,也对离子液体在质谱和光谱中的应用作了介绍。     

Determination of Homologue Imidazolium Ionic Liquid Cations by Ion Chromatography Using a Carboxyl Acid Cation-Exchange Column with Direct Conductivity Detection

An investigation into the determination of four imidazolium ionic liquid cations by ion chromatography using a carboxyl acid cation exchange column and direct conductivity detection was carried out. This research has developed a simple, selective, and accurate ion chromatographic method for separation of imidazolium ionic liquid cations. Detection limits (S/N = 3) for the cations were 3.2–24.3 mg/L. Relative standard deviations (RSD, n = 5) for peak areas were less than 1.6%. The method has been successfully applied to the determination of two ionic liquids synthesized by organic chemistry lab.     

Isotachophoretic separation of selected imidazolium ionic liquids

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

Separation and determination of pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection

A method for rapid and simultaneous determination of multiple pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection was developed.Chromatographic separations were performed on a cation exchange column using ethylenediamine-acetonitrile as the mobile phase.The effects of chromatographic column and the mobile phase,as well as the column temperature on the retention of the cations were investigated.The retention rules of the cations under different chromatographic conditions were formulated.The retention of the cations followed the carbon number rule.The method has been successfully applied to the determination of three ionic liquids synthesized by a chemical laboratory.     

Effect of ultraviolet absorption reagent for determination of piperidinium ionic liquid cations by ion pair chromatography with indirect ultraviolet detection

Indirect ultraviolet detection method is a simple and effective method for the determination of ionic liquid cations without ultraviolet absorption group. This paper focused on the influence of different background ultraviolet absorption reagents on the determination of piperidinium ionic liquid cations by ion pair chromatography with indirect ultraviolet detection. Ultraviolet absorption reagents are divided into cationic (4-aminophenol hydrochloride, 1-ethyl-3-methylimidazolium tetrafluoroborate, and N-ethylpyridinium tetrafluoroborate), anionic (potassium biphthalate and 5-sulfosalicylic acid), and amphiprotic (p-aminobenzoic acid). The results showed that piperidinium cations can be separated and detected by cationic and anionic ultraviolet absorption reagents. In general, the cationic ultraviolet absorption reagents have the best effect for separation and detection of the piperidinium cations by ion pair chromatography with indirect ultraviolet detection.     

Stability of Ag<Superscript>+</Superscript> Complexes with Cryptand 222 in Ionic Liquids

Stability constants of silver(I) complexes with cryptand 222 were measured in a number of ionic liquids, applying potentiometric titration. The ionic liquids were based on 1-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-1-methyl-pyrrolidinium and 1-methyl-1-propyl-pyrrolidinium cations, as well as on tetrafluoroborate, triflate and bis(trifluoromethane sulfonyl) imide. The stability constants, expressed in log K scale, were within the broad range of 8.4–17.2. The formation of the Ag⁺222 cryptates was not detected in ionic liquids based on halide anions. Free enthalpy of silver(I) transfer from dimethylsulfoxide as a reference molecular solvent to ionic liquids was calculated applying the cryptate assumption. The results were discussed in terms of the competition between silver(I) complexation by ion forming ionic liquid and its complexation by cryptand 222.in final form: 6 December 2004This revised version was published online in July 2005 with a corrected issue number.     

Possibilities for removal of chlorinated dye Mordant Blue 9 from model waste water

This comparative study focused on the different methods used for the treatment of model waste water polluted with the chlorinated acid dye Mordant Blue 9. Low-cost and commercially available ionic liquids — benzalkonium chloride and Aliquat 336 — were applied as liquid ion-exchangers to precipitate the Mordant Blue 9 by way of ion pair formation between the bulky ammonium cations of ionic liquids and anions of the above dye. The decolorisation efficiency of the ionic liquid application and the effect on reduction of the absorbance, adsorbable organic halogens, chemical oxygen demand and biological oxygen demand were compared with the conventional coagulation, sorption and Fenton oxidation techniques.