EuCl_3在氯化1-丁基-3-甲基咪唑中的电化学性质

应用循环伏安法研究了Eu3+在亲水性离子液体—氯化1-丁基-3-甲基咪唑([BMIM]Cl)中的电极过程.实验表明,工作电极为玻碳电极时,[BMIM]Cl的电化学窗口为-1.7～0.80V(vs.Ag/AgCl).Eu3+在[BMIM]Cl中被还原为Eu2+,此电极反应受电荷迁移和物质扩散共同控制.当体系温度从55℃升高到75℃时,Eu3+在[BMIM]Cl中的扩散系数D从3.75×10-9cm2/s变化到1.32×10-8cm2/s,该反应活化能Ea为62.6kJ/mol.     

1-丁基-3-甲基咪唑氯化锌离子液体的合成、表征及催化性能

本文合成了1-丁基-3-甲基咪唑氯化锌([BMIM][Zn2Cl5])离子液体,通过红外光谱、TGA、DSC以及1H-NMR等方法对[BMIM][Zn2Cl5]进行了结构表征,实现了对于[BMIM][Zn2Cl5]的定性分析。以尿素醇解合成碳酸二乙酯反应为探针,考查了[BMIM][Zn2Cl5]离子液体的催化性能,结果显示,[BMIM][Zn2Cl5]表现出较好的催化活性及重复利用性能,碳酸二乙酯的收率接近30%。     

氯化镁/氯化1-丁基-3-甲基咪唑改性淀粉/聚丁二酸丁二醇酯共混材料的结构与性能

用氯化镁/氯化1-丁基-3-甲基咪唑([BMIM]Cl)复合增塑剂改性淀粉/聚丁二酸丁二醇酯(PBS)共混材料,采用红外光谱(FTIR)、扫描电子显微镜(SEM)、差示扫描量热分析(DSC)、X射线衍射分析(XRD)及力学性能测试等方法研究了氯化镁/[BMIM]Cl改性淀粉/PBS共混材料的结构和性能.结果表明,氯化镁能与淀粉及PBS形成较强的相互作用,从而破坏淀粉及PBS原有的氢键,导致淀粉/PBS共混体系结构和性能的改变.与[BMIM]Cl改性体系相比,氯化镁/[BMIM]Cl改性体系能进一步增强淀粉与PBS的界面结合力,提高共混体系的相容性;使淀粉/PBS的熔融焓、结晶度及结晶温度降低,冷结晶温度升高;提高共混体系的力学强度和断裂伸长率,抑制[BMIM]Cl因高效增塑产生的强度降低作用.采用氯化镁/[BMIM]Cl改性淀粉/PBS可制备出具有良好力学性能的淀粉/PBS共混材料.     

以[BMIM][Cl]离子液体为添加剂制备普鲁士蓝修饰电极及其电化学催化性质的研究

以氯化1-丁基-3-甲基咪唑离子液体([BMIM][Cl])为溶液添加剂,通过电沉积方法制备了普鲁士蓝(Prussian blue,PB)修饰的碳糊电极(PB-IL/CPE);采用循环伏安法检测了不同[BMIM][Cl]浓度下制备的PB-IL/CPE的电化学性能和动力学特征。同时采用计时安培法检测了PB-IL/CPE对过氧化氢的催化性能。实验结果表明,离子液体的存在能够提高PB在电极表面的沉积电流,[BMIM][Cl]浓度为0.2 mmol/L时,PB的氧化还原电流最大;相对于在无[BMIM][Cl]存在下制备的PB修饰电极(PB/CPE),PB-IL/CPE对过氧化氢的催化效果更好,线性范围更宽,灵敏度更高;此外,PB-IL/CPE电极的动力学特征显示,K+在PB-IL/CPE表面的扩散速率明显提高,为4.45×10-11cm2·s-1。     

对氨基苯酚在石墨烯-离子液体复合物修饰电极上的电化学行为研究

使用石墨烯(Graphene,GR)和离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM] PF6)作修饰剂,通过壳聚糖(CHIT)成膜,制备了石墨烯-离子液体复合物修饰电极([BMIM] PF6 - GR - CHIT/GCE).在0.1 mol/L磷酸盐缓冲液中,采用循环伏安和微分脉冲伏安法研究了对氨基苯酚在[...     

黄芩苷在纳米MnO2-离子液体修饰电极上的电化学性质及电分析方法研究

用疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)和纳米MnO2作修饰剂,通过壳聚糖(CHIT)的成膜效应,构置了玻碳修饰电极([BMIM]PF6-MnO2-CHIT/GCE).在Britton-Robinson(B-R)缓冲液中研究了黄芩苷在修饰电极上的电化学行为,建立了测定黄芩胶囊中黄芩苷含量的...     

293.15K时咪唑醋酸盐-乙醇二元体系的体积性质及分子间相互作用

用比重瓶法测定了293.15 K时1-甲基咪唑醋酸盐([Mim]Ac)/1,3-二甲基咪唑醋酸盐([Mmim]Ac)/1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)-乙醇(EtOH)二元体系在全组成范围内的密度.计算出[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的表观摩尔体积和体系的超额摩尔体积.用三参数多项式关联拟合了表观摩尔体积与摩尔分数的关系,外推出组分的极限偏摩尔体积和摩尔体积.[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的摩尔体积的外推值与实验值分别在±0.07和±0.04 cm3/mol范围内相一致.计算出了[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH分别在无限稀溶液中的溶剂化系数.用Redlich-Kister方程关联拟合了超额摩尔体积与摩尔分数的关系.分别根据极限偏摩尔体积、摩尔体积与极限偏摩尔体积的差值、溶剂化系数和超额摩尔体积对照讨论了分子间相互作用的强弱.结果显示,在[Mim]Ac/[Mmim]Ac/[Emim]Ac的浓度无限稀溶液中,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序为[Mim]Ac-EtOH[Mmim]Ac-EtOH[Emim]Ac-EtOH;在EtOH的浓度无限稀溶液中,以及体系中[Mim]Ac/[Mmim]Ac/[Emim]Ac的摩尔分数在0.15~0.95间时,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序都为[Emim]Ac-EtOH[Mmim]Ac-EtOH[Mim]Ac-EtOH.     

碳纳米管与咪唑类离子液体相互作用机制的理论研究

离子液体(IL)与碳纳米管(CNT)形成的复合体系在许多重要领域有潜在的应用价值,然而人们对于其微观结构的理解尚不清晰,对IL与CNT相互作用机理的认识还存有争议.本文以(8,0)CNT与1-丁基-3-甲基咪唑六氟化磷IL为例研究了CNT与IL的相互作用,分别探讨了1-丁基-3-甲基咪唑阳离子([BMIM+])、六氟化...     

293.15K时咪唑醋酸盐-乙醇二元体系的体积性质及分子间相互作用简

用比重瓶法测定了293.15 K时1-甲基咪唑醋酸盐([Mim]Ac)/1,3-二甲基咪唑醋酸盐([Mmim]Ac)/1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)-乙醇(EtOH)二元体系在全组成范围内的密度. 计算出[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的表观摩尔体积和体系的超额摩尔体积. 用三参数多项式关联拟合了表观摩尔体积与摩尔分数的关系,外推出组分的极限偏摩尔体积和摩尔体积. [Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的摩尔体积的外推值与实验值分别在±0.07和±0.04 cm3/mol范围内相一致. 计算出了[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH分别在无限稀溶液中的溶剂化系数. 用Redlich-Kister 方程关联拟合了超额摩尔体积与摩尔分数的关系. 分别根据极限偏摩尔体积、摩尔体积与极限偏摩尔体积的差值、溶剂化系数和超额摩尔体积对照讨论了分子间相互作用的强弱. 结果显示,在[Mim]Ac/[Mmim]Ac/[Emim]Ac的浓度无限稀溶液中,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序为[Mim]Ac-EtOH>[Mmim]Ac-EtOH >[Emim]Ac-EtOH;在EtOH的浓度无限稀溶液中,以及体系中[Mim]Ac/[Mmim]Ac/[Emim]Ac的摩尔分数在0.15～0.95间时,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序都为[Emim]Ac-EtOH>[Mmim]Ac-EtOH>[Mim]Ac-EtOH.     

咪唑醋酸盐的制备和物理化学性质及其水和乙醇溶液的电导率

制备了离子液体1-甲基咪唑醋酸盐（[Mim]Ac）,1,3-二甲基咪唑醋酸盐（[Mmim]Ac）和1-乙基-3-甲基咪唑醋酸盐（[Emim]Ac）,分别测定了它们在293.15-338.14 K间的密度、电导率和绝对粘度,计算了相应的摩尔电导率和运动粘度.用最小二乘法分别拟合建立了密度、电导率、摩尔电导率、绝对粘度和运动粘度与温度的函数关系.讨论了咪唑环3位氮原子上烷基链长对以上咪唑醋酸盐五种物理化学性质的影响.在293.15 K测定了[Mim]Ac{或[Mmim]Ac,[Emim]Ac}（1）-H₂O（或EtOH）（2）二元溶液在全浓度范围内的电导导率,计算了对应的咪唑醋酸盐的摩尔电导率.发现无论是水溶液还是乙醇溶液,溶液的电导率和咪唑醋酸盐的摩尔电导率都随着浓度的增加先增大而后减小.同一浓度下,咪唑环3位氮原子上烷基链长增加,相应的溶液电导率和摩尔电导率下降.且水溶液的电导率和摩尔电导率远大于乙醇溶液的.     

Dissolution and forming of cellulose with ionic liquids

The dissolution of cellulose in different ionic liquids will be described as a very recent subject for a direct dissolving process, which was used to prepare regenerated cellulose fibres. The preparation of the dopes was arranged starting from slurry of cellulose in the aqueous ionic liquid by removing the water at elevated temperature, vacuum and high shearing rates. As ionic liquids, the 1-N-Butyl-3-methylimidazolium chloride, the 1-Ethyl-3-methylimidazolium chloride, the 1-N-Butyl-2,3-dimethylimidazolium chloride, the 1-N-Butyl-3-methylimidazolium acetate and the 1-Ethyl-3-methylimidazolium acetate were investigated. The cellulose solutions in ionic liquids were characterised by means of light microscopy, cone-plate rheometry and particle analysis. In addition these results were compared with cellulose solutions in N-methyl-morpholine-N-oxide monohydrate. Finally the cellulose dopes were shaped by a dry-wet spinning process to manufacture cellulose fibres. The properties of the resulted fibre had been determined and will be discussed.     

Dissolution and regeneration of polybenzimidazoles using ionic liquids

We report here the initial results that polybenzimidazole can be dissolved in and regenerated from, 1-butyl-3-methylimidazolium chloride and other hydrophilic ionic liquids, which may enable the application of ionic liquids as alternatives to environmentally undesirable solvents currently used for dissolution of this polymer.     

Dissolution of cellulose [correction of cellose] with ionic liquids

We report here initial results that demonstrate that cellulose can be dissolved without activation or pretreatment in, and regenerated from, 1-butyl-3-methylimidazolium chloride and other hydrophilic ionic liquids. This may enable the application of ionic liquids as alternatives to environmentally undesirable solvents currently used for dissolution of this important bioresource.     

共溶剂存在下N-烯丙基吡啶氯盐离子液体对纤维素的溶解性能研究

采用一步法合成N-烯丙基吡啶氯盐离子液体([APy]Cl),考察其对纤维素的溶解性能.结果发现,在120℃下对棉浆粕(聚合度(DP)=556)的溶解度可高达19.71%,但再生后聚合度为223,热降解严重.通过添加不同种类共溶剂的方法克服此缺点.结果表明,有机溶液(DMSO,DMAc,DMF或吡啶)作为[APy]Cl的共溶剂时,[APy]Cl/DMAc复合溶剂对棉浆粕的溶解效果最佳,100℃下溶解度为15.03%,再生后聚合度为403.此外降低了溶剂成本.但70℃下,溶解度仅为1.36%,溶解能力较弱.继续探讨了[AMIM]Cl作为[APy]Cl的共溶剂时对纤维素的溶解性能,结果表明,70℃下,[APy]Cl/[AMIM]Cl复合溶剂对棉浆粕的溶解度为8.78%,再生后聚合度为516.可知添加上述2种共溶剂均使[APy]Cl在低于自身熔点下形成液体并能够溶解一定量纤维素,拓宽了溶解温度区间及应用平台.对FTIR,XRD和TGA谱图分析,结果表明上述为纤维素的直接溶剂,可将其晶型由Ⅰ型转变成Ⅱ型,再生后热稳定性稍有降低.通过照片和SEM表明再生膜无色透明,结构致密.     

1-烯丙基,3-甲基咪唑室温离子液体的合成及其对纤维素溶解性能的初步研究

随着不可再生资源 (如石油、天然气、煤矿和金属矿藏等 )的急剧耗竭 ,天然高分子的开发与利用日益引起世人的关注 .纤维素作为自然界中最丰富的天然高分子材料 ,其开发与利用一直备受关注[1] .但由于天然纤维素较高的结晶度和分子间和分子内存在大量的氢键 ,使其具有不熔化、在大多数溶剂中不溶解的特点 ,这成为纤维素在应用开发中的最大障碍 .开发有效的纤维素溶剂体系是解决这一难题的关键 .研究较多的纤维素溶剂主要有铜氨溶液、Ｎ 甲基吗啉 Ｎ 氧化物(ＮＭＭＯ)溶剂体系 ,氯化锂 二甲基乙酰胺 (ＬｉＣｌ ＤＭＡＣ)溶剂体系等[2 ] ,而这…     

Imidazolium salt assisted hydrolysis of 1-chloro-2,2,2-trifluoroethane

The use of imidazolium-based ionic liquids as promoters was found to be highly effective for the hydrolysis reaction of CF₃CH₂Cl with aqueous potassium acetate to produce 2,2,2-trifluoroethanol (TFE). Among ionic liquids tested, 1-butyl-3-methylimidazolium chloride ([bmim]Cl) showed the highest yield of TFE, over 90%, which is almost two times higher than that obtained in the absence of an ionic liquid. The integrity of imidazolium salt was maintained during the reaction, which was confirmed from the recycling studies and ¹H NMR spectroscopy.     

细菌纤维素在室温离子液体中的溶解性能

研究了细菌纤维素(BC)在绿色溶剂1-烯丙基-3-甲基氯代咪唑室温离子液体中的溶解行为,通过偏光显微镜观察了BC在此离子液体中的溶解过程,热失重(TGA)和红外光谱(FT-IR)测试了再生前后BC的性能,探索了BC在离子液体中溶解、再生的可能性和可行性.结果表明:离子液体是BC的优良溶剂,对BC的溶解属于直接溶解,不发生其他的衍生化反应;再生后BC的热稳定性变好,且离子液体可回收利用.     

Oscillating electrochemical reaction in copper-containing imidazolium ionic liquids

An example of an electrochemical oscillator in ionic liquids is presented. Solutions of the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, which contain both Cu(+) and Cu(2+) ions, show current oscillations during potentiostatic polarization. The oscillations were analyzed by the Quartz Crystal Microbalance (QCM) technique and by Electrochemical Impedance Spectroscopy (EIS). The electrochemical oscillations are of the N-NDR-type, because the low frequency end of the impedance spectrum has negative real impedances. The oscillating current leads to an oscillating growth speed of a metallic copper layer. Besides the presence of both Cu(+) and Cu(2+), the presence of chloride is a necessary, yet not a sufficient, condition for the occurrence of current oscillations. Oscillating currents were also observed for the ionic liquids 1-butyl-3-methylimidazolium chloride and 1-butyl-2,3-dimethylimidazolium chloride, but not for tributyltetradecylphosphonium chloride and N-butylpyridinium chloride.     

Controlling the aqueous miscibility of ionic liquids: aqueous biphasic systems of water-miscible ionic liquids and water-structuring salts for recycle,metathesis, and separations

Hydrophilic ionic liquids can be salted-out and concentrated from aqueous solution upon addition of kosmotropic salts forming aqueous biphasic systems as illustrated by the phase behavior of mixtures of 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) and K3PO4.     

Stereoselective halogenations of alkenes and alkynes in ionic liquids

[reaction: see text]. Room-temperature ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, and 1-butyl-3-methylimidazolium chloride, are used as "green" recyclable alternative to chlorinated solvents for the stereoselective halogenation of alkenes and alkynes.