A Description of the Faradaic Current in Cyclic Voltammetry of Adsorbed Redox Species on Semiconductor Electrodes.

A framework for interpreting the cyclic voltammetric responses from adsorbed redox monolayers on semiconductor electrodes has been developed. Expressions that describe quantitatively how the rates of the forward and back charge-transfer reactions impact the faradaic current density are presented. The primary insight is an explicit connection between the potential drops across the semiconductor space charge, surface, and electrolyte diffuse layers and the potential dependence of the reaction kinetics. Specifically, the evolution of the voltammetric shapes with experimental variables such as scan rate, standard potential of the redox adsorbate, and semiconductor surface energetics can now be interpreted for information on the operative charge-transfer rate constant and reaction energetics. This model is used to understand the complex dependence of the cathodic and anodic wave shapes for the first redox transition of an asymmetric viologen species adsorbed on n-Si(111). This system exhibited a heterogeneous rate constant of 0.24 s -1 and exhibited features consistent with an overwhelming majority of the applied potential dropping within the semiconductor space charge region. In total, experimentalists now have a visual key on how to interpret the faradaic current in voltammetric data for information on heterogeneous charge-transfer reactions between semiconductor electrodes and molecular adsorbates. The presented approach fills a long-standing knowledge gap in electrochemistry and aids practitioners interested in advancing photoelectrochemical energy conversion/storage strategies.