Using Purely Sinusoidal Voltammetry for Rapid Inference of Surface-Confined Electrochemical Reaction Parameters

TY - JOUR

T1 - Using Purely Sinusoidal Voltammetry for Rapid Inference of Surface-Confined Electrochemical Reaction Parameters

AU - Lloyd-Laney, Henry O

AU - Yates, Nicholas D J

AU - Robinson, Martin J

AU - Hewson, Alice R

AU - Firth, Jack D

AU - Elton, Darrell M

AU - Zhang, Jie

AU - Bond, Alan M

AU - Parkin, Alison

AU - Gavaghan, David J

N1 - This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2021/2/2

Y1 - 2021/2/2

N2 - Alternating current (AC) voltammetric techniques are experimentally powerful as they enable Faradaic current to be isolated from non-Faradaic contributions. Finding the best global fit between experimental voltammetric data and simulations based on reaction models requires searching a substantial parameter space at high resolution. In this paper, we estimate parameters from purely sinusoidal voltammetry (PSV) experiments, investigating the redox reactions of a surface-confined ferrocene derivative. The advantage of PSV is that a complete experiment can be simulated relatively rapidly, compared to other AC voltammetric techniques. In one example involving thermodynamic dispersion, a PSV parameter inference effort requiring 7,500,000 simulations was completed in 7 h, whereas the same process for our previously used technique, ramped Fourier transform AC voltammetry (ramped FTACV), would have taken 4 days. Using both synthetic and experimental data with a surface confined diazonium substituted ferrocene derivative, it is shown that the PSV technique can be used to recover the key chemical and physical parameters. By applying techniques from Bayesian inference and Markov chain Monte Carlo methods, the confidence, distribution, and degree of correlation of the recovered parameters was visualized and quantified.

AB - Alternating current (AC) voltammetric techniques are experimentally powerful as they enable Faradaic current to be isolated from non-Faradaic contributions. Finding the best global fit between experimental voltammetric data and simulations based on reaction models requires searching a substantial parameter space at high resolution. In this paper, we estimate parameters from purely sinusoidal voltammetry (PSV) experiments, investigating the redox reactions of a surface-confined ferrocene derivative. The advantage of PSV is that a complete experiment can be simulated relatively rapidly, compared to other AC voltammetric techniques. In one example involving thermodynamic dispersion, a PSV parameter inference effort requiring 7,500,000 simulations was completed in 7 h, whereas the same process for our previously used technique, ramped Fourier transform AC voltammetry (ramped FTACV), would have taken 4 days. Using both synthetic and experimental data with a surface confined diazonium substituted ferrocene derivative, it is shown that the PSV technique can be used to recover the key chemical and physical parameters. By applying techniques from Bayesian inference and Markov chain Monte Carlo methods, the confidence, distribution, and degree of correlation of the recovered parameters was visualized and quantified.

U2 - 10.1021/acs.analchem.0c03774

DO - 10.1021/acs.analchem.0c03774

M3 - Article

C2 - 33417431

SN - 0003-2700

VL - 93

SP - 2062

EP - 2071

JO - Analytical Chemistry

JF - Analytical Chemistry

IS - 4

ER -