Modeling and Experimental Study of the Electron Transfer Kinetics for Non-ideal Electrodes Using Variable-Frequency Square Wave Voltammetry

Aleksei N. Marianov, Alena S. Kochubei, Tanglaw Roman, Oliver J. Conquest, Catherine Stampfl, Yijiao Jiang

Research output: Contribution to journalArticlepeer-review


The knowledge of nonequilibrium electron transfer rates is paramount for the design of modern hybrid electrocatalysts. Herein, we propose a general simulation-based approach to interpret variable-frequency square wave voltammetry (VF-SWV) for heterogeneous materials featuring reversible redox behavior. The resistive and capacitive corrections, inclusion of the frequency domain, and statistical treatment of the surface redox kinetics are used to account for the non-ideal nature of electrodes. This approach has been validated in our study of CoII/CoI redox transformation for Co tetraphenylporphyrin (CoTPP) immobilized on carbon cloth and multiwalled carbon nanotubes (CNTs) - one of the most active heterogeneous molecular catalysts in carbon dioxide (CO2) electroreduction. It is demonstrated that the modeling of experimental data furnishes the capacitance of the surface double layer C, uncompensated resistance Ru, symmetry coefficients α, kinetic constants k0, and equilibrium redox potentials E0 in one experiment. Moreover, the proposed method yields a stochastic map of the redox kinetics rather than a single value, thus exposing the inhomogeneous nature of the electrochemically active layer. The computed parameters are in excellent agreement with the results of the classic methods such as cyclic voltammetry and fall in line with the reported CoTPP catalytic activity. Thus, VF-SWV is suitable for the study of high-level composites such as covalent organic frameworks and organometallic-CNT mixtures. The resulting insights into the electron transfer mechanisms are especially useful for the rational development of the catalyst-support interfaces and immobilization methods.

Original languageEnglish
Pages (from-to)10175-10186
Number of pages12
JournalAnalytical Chemistry
Issue number29
Publication statusPublished - 27 Jul 2021
Externally publishedYes


  • Electron Transfer Kinetics
  • Non-ideal Electrodes
  • Variable-Frequency Square Wave Voltammetry
  • nonequilibrium
  • electron
  • electrocatalysts
  • VF-SWV
  • heterogeneous
  • redox
  • kinetics
  • electrodes


Dive into the research topics of 'Modeling and Experimental Study of the Electron Transfer Kinetics for Non-ideal Electrodes Using Variable-Frequency Square Wave Voltammetry'. Together they form a unique fingerprint.

Cite this