Yuan Wen-Li, Yang Xiao, He Ling, Xue Ying, Qin Song, Tao Guo-Hong
College of Chemistry, Sichuan University, Chengdu, China.
Front Chem. 2018 Mar 15;6:59. doi: 10.3389/fchem.2018.00059. eCollection 2018.
The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([Cmim][N(CN)], [Cmim][N(CN)], N[N(CN)], and N[N(CN)]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation-anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303-333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (), the diffusion coefficients (), the charge transfer rate constants () of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.
离子液体(ILs)的结构-性质关系具有指导意义,可用于新功能化离子液体的特定任务设计。双氰胺(DCA)离子液体是典型的CHN型离子液体,无卤素、化学稳定、低粘度且富含燃料。DCA离子液体的传输性质对于其作为溶剂、电解质和自燃推进剂的应用具有重要意义。本工作系统地研究了四种DCA离子液体([Cmim][N(CN)]、[Cmim][N(CN)]、N[N(CN)]和N[N(CN)])在不同温度下的几种重要传输性质,包括粘度、电导率和电化学性质。熔点、温度依赖性粘度和电导率揭示了四种DCA离子液体的构效关系。从瓦尔登图来看,咪唑阳离子表现出比铵阳离子更强的阳离子-阴离子吸引力。DCA离子液体具有相对较高的电化学窗口(EWs)值,这表明DCA离子液体是电化学应用中电解质的潜在候选物。在303 - 333 K的不同温度下,在GC工作电极上这些DCA离子液体中Eu(III)的循环伏安图由准可逆波组成。DCA离子液体的电化学性质也由阳离子结构主导。Eu(III)在DCA离子液体中的电流强度()、扩散系数()、电荷转移速率常数()均随着摩尔电导率的增加而增加。构建了DCA离子液体的阳离子结构-传输性质关系,以设计新型功能化离子液体来满足特定需求。