Electronic transfer mechanism in self-assembled monolayers of silicon

Garín, Carolina; León, Alejandro; Pacheco, M.; Riveros, G.

doi:10.1007/s10008-019-04400-8

Cited by 1 publication

(1 citation statement)

References 29 publications

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“…Any deviation from this condition could possibly minimize C f . This scenario is not considered here further but may be a property of real systems, where the redox adsorbate has some finite mobility ( 46 – 48 ).…”

Section: Theorymentioning

confidence: 99%

A Gauss’s law analysis of redox active adsorbates on semiconductor electrodes: The charging and faradaic currents are not independent

Vasquez

Waelder

Liu

et al. 2022

Proc. Natl. Acad. Sci. U.S.A.

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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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Section: Theorymentioning

confidence: 99%