University of Texas at Austin , Austin, Texas 78705, United States.
J Am Chem Soc. 2017 May 3;139(17):6114-6119. doi: 10.1021/jacs.6b12104. Epub 2017 Apr 19.
Described here is a semiquantitative theoretical treatment of the kinetics of outer sphere electrochemical reactions. The framework presented here, which is based on simple physical arguments, predicts heterogeneous rate constants consistent with previous experimental observations (k > 10 cm/s). This theory is applied to the analysis of voltammetry experiments involving ultramicroelectrodes modified with thin, insulating oxide films where electronic tunneling between the electrode and redox species in solution (metal-insulator-solution tunneling) is expected to play a prominent role. It is shown that analysis of the voltammetric response of an outer sphere redox couple can be used to track changes in the structure of the adsorbed insulating layer.
这里描述了一种外球电化学反应动力学的半定量理论处理方法。这里提出的框架基于简单的物理论据，预测了与先前实验观察一致的非均相速率常数（k > 10 cm/s）。该理论应用于分析涉及带有薄绝缘氧化膜的超微电极的伏安实验，其中预计电极和溶液中的氧化还原物种之间的电子隧道（金属-绝缘体-溶液隧道）将发挥重要作用。结果表明，可以使用外球氧化还原偶的伏安响应分析来跟踪吸附绝缘层结构的变化。
