傅立叶变换交流伏安法中正弦振幅对热力学色散可视化的影响

IF 3.5 4区 化学 Q2 ELECTROCHEMISTRY
Alister R. Dale-Evans, Dr. Nicholas D. J. Yates, Dr. Rifael Z. Snitkoff-Sol, Prof. Lior Elbaz, Prof. Alan M. Bond, Prof. David J. Gavaghan, Alison Parkin
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引用次数: 0

摘要

伏安实验的数学模型通常包含可逆电位的奇异点值,而表面受限氧化还原活性物质的实验数据通常被解释为包含热力学分散,这意味着电极上的分子种群具有可逆电位值的分布。大振幅斜坡傅立叶变换交流电伏安法(FTacV)是一种将正弦电位时间振荡叠加到线性电位时间斜坡上的技术,已知可以获得大部分没有非法拉第电流的高阶谐波分量。最初,理论研究表明,使用非常大的振幅正弦振荡减少了热力学色散的明显影响;相反,可以改变频率以改变测量对动力学色散的灵敏度。随后,FTacV测量用于探测附着在玻碳电极上的高度热动力学分散的表面约束二茂铁衍生物,其振幅范围为25至300 mV,频率较低,最大限度地减少了动力学分散的影响。实验研究的结果验证了理论预测,表明我们可以在FTacV实验中改变振幅来调节热力学色散。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

The Impact of Sinusoidal Amplitude on Visualising Thermodynamic Dispersion in Fourier Transformed AC Voltammetry

The Impact of Sinusoidal Amplitude on Visualising Thermodynamic Dispersion in Fourier Transformed AC Voltammetry

Mathematical models of voltammetric experiments commonly contain a singular point value for the reversible potential, whereas experimental data for surface-confined redox-active species is often interpreted to contain thermodynamic dispersion, meaning the population of molecules on the electrode possess a distribution of reversible potential values. Large amplitude ramped Fourier Transformed Alternating Current Voltammetry (FTacV), a technique in which a sinusoidal potential-time oscillation is overlaid onto a linear potential-time ramp, is known to provide access to higher order harmonic components that are largely devoid of non-Faradaic current. Initially, a theoretical study reveals that the use of very large amplitude sinusoidal oscillations reduces the apparent effects of thermodynamic dispersion; conversely, frequency can be varied to change the sensitivity of the measurement to kinetic dispersion. Subsequently, FTacV measurements are used to probe a highly thermodynamically dispersed surface-confined ferrocene derivative attached to a glassy carbon electrode, with amplitudes ranging from 25 to 300 mV and low frequency, which minimises the impact of kinetic dispersion. The results from the experimental study validate the theoretical predictions, demonstrating that we can vary the amplitude in FTacV experiments to tune in and out of thermodynamic dispersion.

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来源期刊
ChemElectroChem
ChemElectroChem ELECTROCHEMISTRY-
CiteScore
7.90
自引率
2.50%
发文量
515
审稿时长
1.2 months
期刊介绍: ChemElectroChem is aimed to become a top-ranking electrochemistry journal for primary research papers and critical secondary information from authors across the world. The journal covers the entire scope of pure and applied electrochemistry, the latter encompassing (among others) energy applications, electrochemistry at interfaces (including surfaces), photoelectrochemistry and bioelectrochemistry.
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