半导体
法拉第电流
电极
化学物理
电解质
氧化还原
化学
分析化学(期刊)
电化学
循环伏安法
伏安法
电极电位
材料科学
无机化学
光电子学
物理化学
有机化学
作者
Robert M. Vasquez,Jacob Waelder,Yifan Liu,Hannah Bartels,Stephen Maldonado
标识
DOI:10.1073/pnas.2202395119
摘要
A detailed framework for modeling and interpreting the data in totality from a cyclic voltammetric measurement of adsorbed redox monolayers on semiconductor electrodes has been developed. A three-layer model consisting of the semiconductor space-charge layer, a surface layer, and an electrolyte layer is presented that articulates the interplay between electrostatic, thermodynamic, and kinetic factors in the electrochemistry of a redox adsorbate on a semiconductor. Expressions are derived that describe the charging and faradaic current densities individually, and an algorithm is demonstrated that allows for the calculation of the total current density in a cyclic voltammetry measurement as a function of changes in the physical properties of the system (e.g., surface recombination, dielectric property of the surface layer, and electrolyte concentration). The most profound point from this analysis is that the faradaic and charging current densities can be coupled. That is, the common assumption that these contributions to the total current are always independent is not accurate. Their interrelation can influence the interpretation of the charge-transfer kinetics under certain experimental conditions. More generally, this work not only fills a long-standing knowledge gap in electrochemistry but also aids practitioners advancing energy conversion/storage strategies based on redox adsorbates on semiconductor electrodes.
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