| We synthesized 68 kinds of new aromatic N-heterocycles ligands from benzimidazole, triazole and benzotriazole derivatives and their metal complexes, 125 kinds of different alkyl imidazolium, benzimidazolium and benzotriazolium chloride ionic liquids and their corresponding metal-containing ionic liquids (MILs). These compounds were characterized by elemental analysis, IR spectra, NMR spectra and single crystal X-ray diffraction. The conductivities, thermal analysis, electrochemical behaviors and electrocatalysis of these compounds were studied.1. 58 kinds of new 1-alkyl-1H-benzo[d]imidazole [CnH2n+1-bim](n =3, 4, 5, 8 and 10; bim = benzimidazole) and their metal complexes [M(CnH2n+1-bim)2X2] (M = Co, Cu, Zn, Cd and Fe; X = Cl-, Br-, NO3- and SCN-) were synthesized. Nine crystal structures, such as [Co(C3H7-bim)2Br2], [Cu4(C4H9-bim)4Cl6O], [Zn(C3H7-bim)2Br2] and so on were characterized by single crystal X-ray diffraction. In the range of 20℃to 90℃, we investigated the conductivities of [M(CnH2n+1-bim)2X2] in the different solvents, such as ethanol, acetonitrile, tetrahydrofuran, acetone and N,N'-dimethylformamide. And we discussed the impaction of solvent, alkyl chain and metal salts on the conductivity. Some metal complexes were used as bulk modifier to fabricate carbon paste electrodes. The electrochemical behaviors and electrocatalysis of these modified electrodes had been studied by cyclic voltammetry. These modified electrodes showed good electrocatalytic activities toward the reduction of hydrogen peroxide, nitrite, bromate and trichloroacetic acid (TCA). The possible mechanisms were proposed and the linear range, detection limit and sensitivity were measured.2. 10 kinds of 1-alkyl-1,2,4-triazole and their metal complexes [M(CnH2n+1-taz)2X2] (n = 4 and 10; M = Co and Cu; X = Cl-, Br- and SCN-; taz = triazole), 1-pentyl-1,2,3-benzotriazole and [Zn(C5H11-bta)2Cl2] (bta = benzotriazole), methyl 2-pyridyl ketone oxime and Mn[(2-py)CNOH]2Cl2, Mn[(2-py)CNOH]2(OAc)2 (py = pyridine) were synthesized. The crystal structures of [Cu4(C4H9-taz)4Cl6O], [Zn(C5H11-bta)2Cl2], Mn[(2-py)CNOH]2Cl2 and so on were characterized by single crystal X-ray diffraction. The electrochemical behaviors and electrocatalytic activities of these complexes modified electrodes were characterized by cyclic voltammetry.3. 119 kinds of 1-alkyl-3-methylimidazolium chloride ionic liquid [Cn-mim]Cl(Cn = alkyl chain of CnH2n+1, n = 3, 4, 8, 12, 14, 16 and 18) and the corresponding MILs [Cn-mim]MXm(M = Fe, Co, Cu, Zn, Mn, Cd, La, Ce, Nd and Y; X = Cl-, NO3- and SCN-) were synthesized. The melting points of these MILs were lower than 80℃. The conductivities of these compounds were measured. We discussed the impaction of solvent, alkyl cation, metal ions and anion on the conductivity. The thermal behaviors of [Cn-mim]2[CoCl4] and [Cn-mim]2[CuCl4] (n=14, 16 and 18) were examined by differential scanning calorimetry (DSC) and thermogravimetry (TG). The MILs were used as bulk modifier to fabricate carbon paste electrodes (MIL/CPE) and had double functions of a binder and an electrocatalyst. The MIL/CPE showed good electrocatalytic activities toward the reduction of hydrogen peroxide, nitrite, bromate, iodate and trichloroacetic acid. These modified electrodes had good reproducibility, high stability, low detection limit, technical simplicity and possibility of rapid preparation.4. The metal-containing ionic liquid of 1,3-dialkylbenzimidazole [(C3H7)2-bim]2[CdCl4], [(C10H21)2-bim]2[Cd2Cl6] and 1,3-dibutylbenzotriazole chloride ionic liquid and [(C4H9)2-bta][(C4H9-bta)CdCl3] (bta = benzotriazole) were synthesized. The crystal structures of three MILs were characterized by single crystal X-ray diffraction. We studied the thermal stability and conductivities of them. They were also used as bulk modifier to fabricate carbon paste electrodes. The electrochemical behaviors and electrocatalytic properties of these modified carbon paste electrodes had been studied by cyclic voltammetry.
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