萃取体系二相界面荷电物质传输的电化学研究 I: 邻菲咯啉体系中Ni(II)、Co(II)相转移的电化学性质

用线性电流扫描极谱、恒电流单阶跃计时电位法及等电流双阶跃计时电位法, 研究了Ni(II)、Co(II)-邻菲咯啉(phen)体系在1,2-二氯乙烷(DCE)/水界面相转移的电化学行为。同时, 研究了相转移过程的机理。结果表明, 电解前, Phen与Ni(II)或Co(II)同时在水相时, Ni(II)、Co(II)行为类同; 若电解前Phen在有机相时, Ni(II)、Co(II)的行为截然不同, 原因在于两者与Phen配位反应的动力学的差异。     

功能化离子液体中Ag纳米微粒的制备及摩擦学性能研究

合成了1-甲基-3-羟乙基咪唑四氟硼酸盐离子液体([C₂OHmim]BF₄)，用红外光谱表征了其结构。以所合成的离子液体作为还原剂、稳定剂与反应介质制备了Ag纳米微粒，用XRD和TEM对微粒的结构和形貌进行了表征。在四球摩擦磨损实验机上研究了[C₂OHmim]BF₄离子液体及掺入Ag纳米微粒后的离子液体的摩擦学性能。掺入银纳米微粒后，离子液体在高载荷下的润滑性有了大幅的改善。用SEM和XPS分别对磨痕表面的形貌和元素组成、化学状态进行了分析，结果表明：在低、高载荷分别起润滑作用的是有机膜和金属-有机复合膜。     

Facile Synthesis of Ureas in lonic Liquid

The reaction of isocyanates with aliphatic and aromatic amines in the l-n-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) ionic liquid in good to excellent yields is described.Due to its insolubility, the desired urea solids could be recovered by simple filtration from the ionic liquid after reaction.     

离子液体介导CO2化学转化研究进展

The efficient utilization of carbon dioxide (CO₂) as a C1 feedstock is of great significance for green and sustainable development. Therefore, the efficient chemical conversion of CO₂ into value-added products has recently attracted a lot of research attention in recent years. The transformation of CO₂ generally requires high-energy substrates, specific catalysts, and harsh reaction conditions due to its high thermodynamic stability and kinetic inertness. Consequently, several efforts have been dedicated toward the development of high-performance catalysts and new reaction routes for CO₂ conversion over the last few decades. To date, many routes of convert CO₂ into value-added chemicals have been proposed, together with the development of heterogeneous and homogeneous catalysts. Among the advanced catalysts reported to date, ionic liquids (ILs) have been widely investigated and show great potential for the efficient, selective, and economical conversion of CO₂ into highly valuable products under mild conditions, even under ambient conditions. Some task-specific ILs have been designed with unique functional groups (e.g., —OH, —SO₃H, —NH₂, —COOH, and —C≡N), which can act as the solvent, absorbent, activating agent, catalyst, or cocatalyst to realize the transformation of CO₂ under metal-free and mild conditions. In addition, a variety of catalytic systems composed of ILs and metal catalysts have also been reported for the transformation of CO₂, in which the combination of the IL and metal catalyst is responsible for CO₂ conversion with high efficiency. In this review article, we summarize the recent advances in IL-mediated CO₂ transformation into chemicals prepared via C—O, C—N, C—S, C—H, and C—C bond forming processes. ILs that can chemically capture CO₂ with high capacity are first introduced, which can activate CO₂ via the formation of IL-based carbonates or carbamates, thus realizing the transformation of CO₂ under metal-free and mild conditions. Recent progress in IL-mediated CO₂ transformations to form carbonates and various kinds of N- and S-containing compounds (e.g., oxazolidinones, ureas, benzimidazolones, formamides, methylamines, benzothiazoles, and other chemicals) as well as CO₂ hydrogenation to give formic acid, methane, acetic acid, low-carbon alcohols, and hydrocarbons has been summarized in this review with a focus on the reaction routes, catalytic systems, and reaction mechanism. In these reactions, ILs can simultaneously activate the substrate via strong H-bonding in addition to activating CO₂, and the cooperative effects among the ionic and molecular species and metal catalysts accomplish the reactions of CO₂ with various kinds of substrates to afford a wide range of value-added chemicals. Finally, the shortcomings and perspectives of ILs are discussed. In short, IL-mediated CO₂ transformations provide green and effective routes for the synthesis of high-value chemicals, which may have great potential for a wide range of applications.     

功能液晶膜的新进展

论述了功能液晶膜的新近研究结果和发展动向,指出功能液晶膜具有优异的气体分离、液体分离和电光性能,可望作为高效气体分离膜、高效液体分离膜和大面积光控膜,具有较重大的理论与实际意义。     

Novel Synthesis of 1,2,3-Triazoles via 1,3-Dipolar Cycloadditions of Alkynes to Azides in Ionic Liquid^＋

2-Azido-3,5-dichloropyridine and 2-azido-5-chloro-3-fluoropyridine were given by reaction of sodium azide with 2,3,5-trichloropyridine, 3,5-dichloro-2-fluoropyridine or 5-chloro-2,3-difluoropyridine in ionic liquids. 1,3-Dipolar cycloaddition of 2-azido-3,5-dichloropyridine or 2-azido-5-chloro-3-fluoropyridine to alkynes in ionic liquids afforded the corresponding 1,4,5-trisubstituted [1,2,3]-triazoles in good yields and regioselectivities.     

[Bmim]Br3对酮的选择性单溴化反应

在无溶剂和室温条件下, 三溴化1-丁基-3-甲基咪唑([Bmim]Br₃)选择性地与酮反应, 以90%～96%的产率生成相应的α-溴代酮. 该方法反应条件温和、产率高、选择性好、环境友好.     

Synthesis of N-（α-Alkoxyalkyl）benzotriazoles Catalyzed by Acidic Ionic Liquid at Room Temperature

N-（α-Alkoxyalkyl）benzotriazoles were synthesized via the condensation of benzotriazole with various aldehydes and alcohols catalyzed by acidic ionic liquid [hmim]HSO4 at room temperature. The yield was up to 99%. This novel method was effective when triethoxymethane was utilized instead of alcohols. Moreover, acidic ionic liquid could be reused easily with no significant degradation of its catalytic activity.     

烷基吡啶及氯化铝正负离子结构的密度泛函研究

采用量子化学密度泛函方法对N-烷基吡啶阳离子和阴离子AlCl4-,Al2Cl7-和Al3Cl10-进行了全优化计算,得到了阴阳离子的几何构型和净电荷分布.计算发现,吡啶环上的电子数符合4n 2规则,具有芳香性.吡啶阳离子的LUMO轨道主要由环上原子的2pz所贡献,是反键π分子轨道.AlCl4-,Al2Cl7-和Al3Cl10-的HOMO轨道主要由Cl原子的2px所贡献.推测吡啶阳离子的LUMO与阴离子的HOMO相互作用形成离子液体分子.     

氯铝酸室温离子液体介质中正碳十二烯选择环化反应

 在氯化1－丙基－3－甲基咪唑（PMImCl）、氯化1－丁基－3－甲\r\n基咪唑（BMImCl）、氯化1－丁基吡啶（BPCl）和溴化1－乙基吡啶（E\r\nPBr）季铵盐与AlCl3构成的室温离子液体介质中，首次发现正十二碳烯\r\n（简称十二烯）可以高选择性地发生环化反应生成环十二烷．依次在反\r\n应管中加入氯铝酸室温离子液体、乙醇和十二烯，其中AlCl3的量为0．\r\n01mol，AlCl3与季铵盐的摩尔比为2，乙醇为10ml，十二烯为2ml（9．\r\n3mmol）．当反应体系中不添加乙醇时，十二烯转化率和环十二烷选择\r\n性仅分别为4．2％和73．1％．这是由于十二烯和氯铝酸离子液体形成\r\n两相体系而不易充分接触，故十二烯转化率和环十二烷选择性较低．当\r\n反应体系中加入乙醇时，十二烯和氯铝酸离子液体体系变为单相，使得\r\n十二烯和氯铝酸离子液体可以充分接触，十二烯转化率和环十二烷选择\r\n性可分别达到12．4％和82．9％．压力对提高十二烯转化率和环十二烷\r\n选择性有很大的影响．p（N2）＝3．0～6．0MPa下反应12h，十二烯转\r\n化率和环十二烷选择性可分别达到27．2％和93．8％．反应结束后加热\r\n除去乙醇，产物自动与离子液体分层，便于分离，且离子液体介质可重\r\n复使用．