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

Vasquez, Robert; Waelder, Jacob; Liu, Yifan; Bartels, Hannah; Maldonado, Stephen

doi:10.1073/pnas.2202395119

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

Journal Article · Mon Aug 29 00:00:00 EDT 2022 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2202395119· OSTI ID:1884353

Vasquez, Robert ^[1]; Waelder, Jacob ^[2]; Liu, Yifan ^[3]; Bartels, Hannah ^[1]; ^[4]

Department of Chemistry, University of Michigan, Ann Arbor, MI 48105-1055
Program in Applied Physics, University of Michigan, Ann Arbor, MI 48109-1055
Electrical Engineering and Computer Science, University of Michigan, Ann Arbor, MI 48105-1055
Department of Chemistry, University of Michigan, Ann Arbor, MI 48105-1055, Program in Applied Physics, University of Michigan, Ann Arbor, MI 48109-1055

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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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0006628

OSTI ID:: 1884353

Alternate ID(s):: OSTI ID: 1979173

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 36 Vol. 119; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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