Department of Chemistry, Georgia State University, Atlanta, Georgia 30303, USA.
Anal Chem. 2010 Jun 1;82(11):4520-8. doi: 10.1021/ac100440z.
Mass transport through an interfacial area at nanometer scale is a key process to be addressed in research and applications employing nanostructured electrodes, nanofluidic devices, and high surface area materials. Ionic transport through single glass nanopores is investigated by multifrequency impedance techniques. The conical glass nanopores display current rectification under controlled experimental conditions in voltammetric studies. Being inaccessible by conductivity and DC voltammetry, phase sensitive capacitive and "inductive" components in the two-dimensional impedance spectrum reveal dynamic ionic transport information. The nanopore impedance responses are strongly influenced by the concentration of electrolytes and are correlated with current rectification. Multitime-constant impedance loops are detected in different frequency ranges. The multitime-constant features are attributed to the negative charges at the glass-solution interface. The impedance data are interpreted by designed equivalent circuit models. With the correlation of experimental and modeling results established, current signals can be differentiated into two categories: those originated from ionic transport affected by the immobilized charges at the solid-solution interface and those resulted from the applied waveform with ionic transport governed by geometric factors such as the radius of the nanopore.
纳米尺度界面区域的物质传输是采用纳米结构电极、纳流控装置和高表面积材料的研究和应用中需要解决的关键过程。通过多频阻抗技术研究了离子通过单玻璃纳米孔的传输。在伏安研究中,在受控实验条件下,圆锥形玻璃纳米孔显示出电流整流。由于电导率和直流伏安法不可用,二维阻抗谱中的相敏电容和“感应”分量揭示了动态离子传输信息。纳米孔阻抗响应强烈受电解质浓度的影响,并与电流整流相关。在不同频率范围内检测到多时间常数阻抗环。多时间常数特征归因于玻璃-溶液界面处的负电荷。阻抗数据通过设计的等效电路模型进行解释。通过建立实验和建模结果的相关性,可以将电流信号分为两类:一类是由固-液界面固定电荷影响的离子传输产生的信号,另一类是由施加的波形产生的信号,离子传输受纳米孔半径等几何因素控制。