Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, United Kingdom OX1 3QZ.
Phys Chem Chem Phys. 2010 Feb 28;12(8):1827-33. doi: 10.1039/b920217j. Epub 2009 Dec 10.
The Sn/Sn(II) couple is studied in the room temperature ionic liquids N-butyl-N-methylpyrrolidinium dicyanamide, [C(4)mpyrr][N(CN)(2)] and N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C(4)mpyrr][NTf(2)] using cyclic voltammetry. The Sn(II) species is introduced into each of the ionic liquids by dissolving either SnCl(2) or Sn(CF(3)SO(3))(2). The diffusion coefficient of the Sn(II) species produced is found to vary with the ionic liquid, partly reflecting the difference in the viscosity of the two liquids, but also to vary with the Sn(II) salts used, indicating that different Sn(II) species may be present. The mechanism for the stripping of deposited tin is found to change with potential and also vary with the Sn(II) salt/ionic liquid combination used. In [C(4)mpyrr][N(CN)(2)] the mechanism for the tin stripping process is broadly similar for both of the Sn(II) salts used indicating that the morphology of the tin deposit is similar and that the stripping mechanism is largely independent of the Sn(II) salt anion. In [C(4)mpyrr][NTf(2)] a large difference was seen in the voltammetry of the different Sn(II) salts. Tafel analysis is used to show that the mechanism of the oxidation of Sn is sensitive to the solvent, the salt and the potential. The rate determining step was found to vary between the first electron transfer, the second electron transfer and a step likely involving reactions of a Sn(+) intermediate.
采用循环伏安法研究了室温离子液体 N-丁基-N-甲基吡咯烷二氰胺 [C(4)mpyrr][N(CN)(2)] 和 N-丁基-N-甲基吡咯烷双(三氟甲基磺酰基)亚胺 [C(4)mpyrr][NTf(2)] 中的 Sn/Sn(II) 电对。通过溶解 SnCl2 或 Sn(CF3SO3)2 将 Sn(II)物种引入到每种离子液体中。发现生成的 Sn(II)物种的扩散系数随离子液体而变化,部分反映了两种液体的粘度差异,但也随所用的 Sn(II)盐而变化,表明可能存在不同的 Sn(II)物种。发现沉积锡的剥离机制随电位变化,也随所用的 Sn(II)盐/离子液体组合而变化。在 [C(4)mpyrr][N(CN)(2)] 中,两种 Sn(II)盐均用于剥离过程的机制大致相似,表明锡沉积物的形态相似,剥离机制在很大程度上独立于 Sn(II)盐阴离子。在 [C(4)mpyrr][NTf(2)] 中,不同 Sn(II)盐的伏安法存在很大差异。塔菲尔分析用于表明 Sn 氧化的机制对溶剂、盐和电位敏感。发现速率决定步骤在第一电子转移、第二电子转移和可能涉及 Sn(+)中间体反应的步骤之间变化。