Growth and Morphology of Liquid Phase in Frozen Aqueous NaCl Probed by Voltammetric Measurements and Simulations
Growth and Morphology of Liquid Phase in Frozen Aqueous NaCl Probed by Voltammetric Measurements and Simulations
复制标题
通过伏安测量和模拟探测冷冻氯化钠水溶液中液相的生长和形态
DOI：
10.1002/cphc.201800788
复制
发表时间：
2018
期刊：
影响因子：
2.9
通讯作者：
Makoto Harada,Tetsuo Okada
中科院分区：
文献类型：
--
作者：
Yoshiharu Fukui;Akihisa Miyagawa;Hui Qu;Makoto Harada,Tetsuo Okada
使用微电极在冷冻NaCl水溶液中测量Fe(CN)64−的循环伏安图（cv），以获得电极表面形成的液相的形态信息。在某些情况下，冷冻溶液中的cv具有与在散装溶液中测量的相似的径向扩散，但在其他情况下则具有线性扩散。前者意味着液相的充分生长，而后者意味着特定方向的扩散路径受到阻碍。两个参数，即。从CVs中提取出最大电流与稳态电流(R)和电流放大（斜坡）的比值，并与模拟值进行比较。对四种几何模型进行了CV仿真。从ramand和r的关系来看，在电极表面发育的FCS可以看作是平行于电极表面方向发育的薄层或远离电极方向运行的圆柱体。由于溶质集中在液相中，如果成功地管理了FCS的生长，则可以进行高灵敏度的伏安分析。电极上的液相形态是其他方法无法探测到的，是设计这种高灵敏度伏安分析的有用信息。
Cyclic voltammograms (CVs) of Fe(CN)64−are measured using a microelectrode in frozen aqueous NaCl solutions to obtain morphological information on the liquid phase developed on the electrode surface. CVs in frozen solutions feature the radial diffusion similar to that measured in bulk solution in some cases but the linear diffusion in other cases. The former suggests the sufficient growth of the liquid phase, whereas the latter implies the diffusion paths in particular directions are hindered. Two parameters, i. e. a ratio of the maximum current to the steady‐state current (R) and current amplification (ramp), are extracted from CVs and compared with those of simulated ones. CV simulations are carried out for four geometrical models. From the relationship betweenrampandR, the FCS developed on the electrode surface can be regarded as a thin layer developed in the direction parallel to the electrode surface or a cylinder running in the direction away from the electrode. Since solutes are concentrated in this liquid phase, highly sensitive voltammetric analysis would be possible if the growth of the FCS were successfully managed. The liquid phase morphology on the electrode, which cannot be probed by other methods, is useful information for designing such highly sensitive voltammetric analyses.