Practical Guide to Large Amplitude Fourier-Transformed Alternating Current Voltammetry─What, How, and Why

IF 4.6 Q1 CHEMISTRY, ANALYTICAL ACS Measurement Science Au Pub Date : 2024-05-07 DOI:10.1021/acsmeasuresciau.4c00008
Natalia G. Baranska, Bryn Jones, Mark R. Dowsett, Chris Rhodes, Darrell M. Elton, Jie Zhang, Alan M. Bond, David Gavaghan, Henry O. Lloyd-Laney, Alison Parkin
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Abstract

Fourier-transformed alternating current voltammetry (FTacV) is a technique utilizing a combination of a periodic (frequently sinusoidal) oscillation superimposed onto a staircase or linear potential ramp. The advanced utilization of a large amplitude sine wave induces substantial nonlinear current responses. Subsequent filter processing (via Fourier-transformation, band selection, followed by inverse Fourier-transformation) generates a series of harmonics in which rapid electron transfer processes may be separated from non-Faradaic and competing electron transfer processes with slower kinetics. Thus, FTacV enables the isolation of current associated with redox processes under experimental conditions that would not generate meaningful data using direct current voltammetry (dcV). In this study, the enhanced experimental sensitivity and selectivity of FTacV versus dcV are illustrated in measurements that (i) separate the Faradaic current from background current contributions, (ii) use a low (5 μM) concentration of analyte (exemplified with ferrocene), and (iii) enable discrimination of the reversible [Ru(NH3)6]3+/2+ electron-transfer process from the irreversible reduction of oxygen under a standard atmosphere, negating the requirement for inert gas conditions. The simple, homebuilt check-cell described ensures that modern instruments can be checked for their ability to perform valid FTacV experiments. Detailed analysis methods and open-source data sets that accompany this work are intended to facilitate other researchers in the integration of FTacV into their everyday electrochemical methodological toolkit.

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大振幅傅立叶变换交流伏安法实用指南--内容、方法和原因
傅立叶变换交流伏安法(FTacV)是一种将周期性(通常为正弦波)振荡叠加到阶梯或线性电位斜坡上的技术。对大振幅正弦波的先进利用会诱发大量非线性电流响应。随后的滤波处理(通过傅立叶变换、波段选择和反傅立叶变换)会产生一系列谐波,在这些谐波中,快速电子传递过程可以与非法拉第电子传递过程和动力学较慢的竞争电子传递过程区分开来。因此,FTacV 能够在使用直流伏安法(dcV)无法产生有意义数据的实验条件下,分离出与氧化还原过程相关的电流。在本研究中,FTacV 相对于 dcV 的更高实验灵敏度和选择性体现在以下测量中:(i) 将法拉第电流从背景电流贡献中分离出来;(ii) 使用低(5 μM)浓度的分析物(以二茂铁为例);(iii) 在标准大气环境下将可逆的[Ru(NH3)6]3+/2+ 电子转移过程与不可逆的氧气还原过程区分开来,从而消除了对惰性气体条件的要求。所述简单的自制检查电池可确保检查现代仪器是否能够进行有效的 FTacV 实验。这项工作所附带的详细分析方法和开源数据集旨在帮助其他研究人员将 FTacV 纳入他们的日常电化学方法工具包。
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ACS Measurement Science Au
ACS Measurement Science Au 化学计量学-
CiteScore
5.20
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0.00%
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0
期刊介绍: ACS Measurement Science Au is an open access journal that publishes experimental computational or theoretical research in all areas of chemical measurement science. Short letters comprehensive articles reviews and perspectives are welcome on topics that report on any phase of analytical operations including sampling measurement and data analysis. This includes:Chemical Reactions and SelectivityChemometrics and Data ProcessingElectrochemistryElemental and Molecular CharacterizationImagingInstrumentationMass SpectrometryMicroscale and Nanoscale systemsOmics (Genomics Proteomics Metabonomics Metabolomics and Bioinformatics)Sensors and Sensing (Biosensors Chemical Sensors Gas Sensors Intracellular Sensors Single-Molecule Sensors Cell Chips Arrays Microfluidic Devices)SeparationsSpectroscopySurface analysisPapers dealing with established methods need to offer a significantly improved original application of the method.
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