Demonstration of Superiority of the Marcus-Hush Electrode Kinetic Model in the Electrochemistry of Dissolved Decamethylferrocene at a Gold Modified Electrode by Fourier Transformed Alternating Current Voltammetry

Jiezhen Li, Gareth F Kennedy, Alan M Bond, Jie Zhang

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Fourier-transformed alternating current (AC) voltammetry is used to compare the applicability of the Butler-Volmer (BV) and Marcus-Hush (MH) models of electrode kinetics (k0) to an outer-sphere electrode process where both oxidized and reduced species are soluble. According to numerical simulations, differences between the two models can be revealed clearly by analysis of the AC harmonics when the values of k0 and reorganization energy are sufficiently small. Experimentally a Au electrode coated with a self-assembled octanethiol monolayer was introduced to decrease the rate of the DmFc0/+ (DmFc = decamethylferrocene) process, a well-known outer-sphere process in a propylene carbonate solution containing 0.10 M tetrapropylammonium tetrafluoroborate. Based on a comparison of the computationally generated best fits, it was demonstrated that the MH model provides substantially better agreement with the experimental data than the BV model for the DmFc0/+ process, unlike some other examples in the literature that favor the BV model.

Original languageEnglish
Pages (from-to)9009-9014
Number of pages6
JournalJournal of Physical Chemistry C
Volume122
Issue number16
DOIs
Publication statusPublished - 26 Apr 2018

Cite this

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title = "Demonstration of Superiority of the Marcus-Hush Electrode Kinetic Model in the Electrochemistry of Dissolved Decamethylferrocene at a Gold Modified Electrode by Fourier Transformed Alternating Current Voltammetry",
abstract = "Fourier-transformed alternating current (AC) voltammetry is used to compare the applicability of the Butler-Volmer (BV) and Marcus-Hush (MH) models of electrode kinetics (k0) to an outer-sphere electrode process where both oxidized and reduced species are soluble. According to numerical simulations, differences between the two models can be revealed clearly by analysis of the AC harmonics when the values of k0 and reorganization energy are sufficiently small. Experimentally a Au electrode coated with a self-assembled octanethiol monolayer was introduced to decrease the rate of the DmFc0/+ (DmFc = decamethylferrocene) process, a well-known outer-sphere process in a propylene carbonate solution containing 0.10 M tetrapropylammonium tetrafluoroborate. Based on a comparison of the computationally generated best fits, it was demonstrated that the MH model provides substantially better agreement with the experimental data than the BV model for the DmFc0/+ process, unlike some other examples in the literature that favor the BV model.",
author = "Jiezhen Li and Kennedy, {Gareth F} and Bond, {Alan M} and Jie Zhang",
year = "2018",
month = "4",
day = "26",
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language = "English",
volume = "122",
pages = "9009--9014",
journal = "Journal of Physical Chemistry C",
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publisher = "American Chemical Society",
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TY - JOUR

T1 - Demonstration of Superiority of the Marcus-Hush Electrode Kinetic Model in the Electrochemistry of Dissolved Decamethylferrocene at a Gold Modified Electrode by Fourier Transformed Alternating Current Voltammetry

AU - Li, Jiezhen

AU - Kennedy, Gareth F

AU - Bond, Alan M

AU - Zhang, Jie

PY - 2018/4/26

Y1 - 2018/4/26

N2 - Fourier-transformed alternating current (AC) voltammetry is used to compare the applicability of the Butler-Volmer (BV) and Marcus-Hush (MH) models of electrode kinetics (k0) to an outer-sphere electrode process where both oxidized and reduced species are soluble. According to numerical simulations, differences between the two models can be revealed clearly by analysis of the AC harmonics when the values of k0 and reorganization energy are sufficiently small. Experimentally a Au electrode coated with a self-assembled octanethiol monolayer was introduced to decrease the rate of the DmFc0/+ (DmFc = decamethylferrocene) process, a well-known outer-sphere process in a propylene carbonate solution containing 0.10 M tetrapropylammonium tetrafluoroborate. Based on a comparison of the computationally generated best fits, it was demonstrated that the MH model provides substantially better agreement with the experimental data than the BV model for the DmFc0/+ process, unlike some other examples in the literature that favor the BV model.

AB - Fourier-transformed alternating current (AC) voltammetry is used to compare the applicability of the Butler-Volmer (BV) and Marcus-Hush (MH) models of electrode kinetics (k0) to an outer-sphere electrode process where both oxidized and reduced species are soluble. According to numerical simulations, differences between the two models can be revealed clearly by analysis of the AC harmonics when the values of k0 and reorganization energy are sufficiently small. Experimentally a Au electrode coated with a self-assembled octanethiol monolayer was introduced to decrease the rate of the DmFc0/+ (DmFc = decamethylferrocene) process, a well-known outer-sphere process in a propylene carbonate solution containing 0.10 M tetrapropylammonium tetrafluoroborate. Based on a comparison of the computationally generated best fits, it was demonstrated that the MH model provides substantially better agreement with the experimental data than the BV model for the DmFc0/+ process, unlike some other examples in the literature that favor the BV model.

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U2 - 10.1021/acs.jpcc.8b01324

DO - 10.1021/acs.jpcc.8b01324

M3 - Article

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SP - 9009

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JO - Journal of Physical Chemistry C

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