Attributes of Large‐Amplitude Fourier Transformed Alternating Current Voltammetry at Array and Single Carbon Fiber Microdisk Electrodes

Lee, Chong; Elton, Darrell; Brajter-Toth, Anna; Bond, Alan M.

doi:10.1002/elan.201200338

Cited by 5 publications

(5 citation statements)

References 30 publications

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“…48 Importantly, the optimal kinetically sensitive range of regime II achievable with FTACV is higher than that with DCCV (for the same DC potential sweep scan rate) and is tunable by changing f. Increasing ΔE also increases the accessibility of higher AC harmonic components. 49 Higher kinetic sensitivity can be achieved by increasing the scan rate in DCCV but is accompanied by an increase in double layer charging that reduces the reliability of the measurements and requires multiple experiments. 46 Use of higher order AC harmonic components, in contrast, allows measurements to be made that are devoid of charging current, and all data are obtained from a single experiment.…”

Section: ■ the Technique Of Ftacvmentioning

confidence: 99%

Probing Electrode Heterogeneity Using Fourier-Transformed Alternating Current Voltammetry: Application to a Dual-Electrode Configuration

et al. 2017

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Quantitative studies of electron transfer processes at electrode/electrolyte interfaces, originally developed for homogeneous liquid mercury or metallic electrodes, are difficult to adapt to the spatially heterogeneous nanostructured electrode materials that are now commonly used in modern electrochemistry. In this study, the impact of surface heterogeneity on Fourier-transformed alternating current voltammetry (FTACV) has been investigated theoretically under the simplest possible conditions where no overlap of diffusion layers occurs and where numerical simulations based on a 1D diffusion model are sufficient to describe the mass transport problem. Experimental data that meet these requirements can be obtained with the aqueous [Ru(NH)] redox process at a dual-electrode system comprised of electrically coupled but well-separated glassy carbon (GC) and boron-doped diamond (BDD) electrodes. Simulated and experimental FTACV data obtained with this electrode configuration, and where distinctly different heterogeneous charge transfer rate constants (k values) apply at the individual GC and BDD electrode surfaces, are in excellent agreement. Principally, because of the far greater dependence of the AC current magnitude on k, it is straightforward with the FTACV method to resolve electrochemical heterogeneities that are ∼1-2 orders of magnitude apart, as applies in the [Ru(NH)] dual-electrode configuration experiments, without prior knowledge of the individual kinetic parameters (k and k) or the electrode size ratio (θ:θ). In direct current voltammetry, a difference in k of >3 orders of magnitude is required to make this distinction.

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Section: ■ the Technique Of Ftacvmentioning

confidence: 99%

Probing Electrode Heterogeneity Using Fourier-Transformed Alternating Current Voltammetry: Application to a Dual-Electrode Configuration

et al. 2017

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“…The oxidation of 1 mM ferrocenemethanol was performed in aqueous solution without and with increasing amounts of KCl added as supporting electrolyte. The reversible potential or E1/2 value for the one-electron oxidation of ferrocenemethanol [28] (equation 3) is at 0.20 V vs. Ag/AgCl.…”

Section: Supporting Electrolyte Effects On Dual-plate Sensor Signal Imentioning

confidence: 99%

Dual-Plate Gold-Gold Microtrench Electrodes for Generator-Collector Voltammetry without Supporting Electrolyte

Montiel

Iniesta

Gross

et al. 2017

Electrochimica Acta

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A gold-gold dual-plate microtrench electrode system based on two oppositely placed gold surfaces with 5 mm length, 17 m average depth, and 6 m inter-electrode gap is employed in generator-collector configuration in a four-electrode cell (counter electrode, reference electrode, and two independent working electrodes denoted "generator"with scanning potential-and "collector"with fixed potential). The dual-plate microtrench electrodes were investigated for (i) the reduction of Ru(NH3)6 3+ , (ii) the oxidation of ferrocenemethanol, and (iii) the oxidation of iodide in aqueous media, all as a function of supporting electrolyte concentration. It is shown that due to the inter-electrode feedback character of the generator-collector currents, well-defined steady state sensor responses are obtained for the collector electrode even in the absence of added electrolyte. The variation in the mass transport limited steady state current (measured at the collector electrode) with addition/removal of supporting electrolyte remains low (compared to unexpectedly stronger effects caused by the switch between reduction and oxidation conditions at the collector electrode). Microtrench electrode systems are suggested for sensing applications without/with varying levels of supporting electrolyte.

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“…They observed that high harmonics were highly sensitive to electron transfer kinetics [12] and this sensitivity allows separation of the electron‐transfer reaction of interest from the catalytic current in the frequency domain [13]. These kinetic studies were utilized to evaluate high harmonics of ferrocenemethanol and uric acid [14], and used for analytical determination of those analytes using a carbon microdisks electrode [12b]. Later, the Oldham group has identified concordance between semiintegral of the harmonic response and the amplitude of the current to understand how reversible reaction responses in FT‐ACV (Fourier transformed alternating current voltammetry‐sine wave superimposed on a linear ramp) [15].…”

Section: Introductionmentioning

confidence: 99%

A Comprehensive Examination of Voltammetric Parameters in Fourier Transform Sine‐wave Voltammetry (FT‐SWV) Leading to Concentration Linearity and High Signal‐to‐background Ratio

Yang

Weber

2022

Electroanalysis

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There has not been a comprehensive investigation of the effect of voltammetric parameters: amplitude, dc bias potential, and excitation frequency of the sine waveform in Fourier Transform Sine-Wave Voltammtery (FT-SWV) on background, signal, and signal-to-background ratio as well as linearity with respect to the concentration of an analyte. FT-SWV of ruthenium hexamine (III) chloride (RuHex) demonstrates that the dc bias potential can be used to adjust the phase angle difference between the signal and background to obtain out-of-phase background. Several conditions show a high signal-to-noise ratio and good concentration linearity. The lessons from RuHex guided us to conditions for good signal-to-background ratio and concentration linearity for dopamine (DA). Keywords: sine-wave voltammetry • FT-SWV • signal-to-background ratio • phase-sensitive detection • out-of-phase background [a] Y.

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Attributes of Large‐Amplitude Fourier Transformed Alternating Current Voltammetry at Array and Single Carbon Fiber Microdisk Electrodes

Cited by 5 publications

References 30 publications

Probing Electrode Heterogeneity Using Fourier-Transformed Alternating Current Voltammetry: Application to a Dual-Electrode Configuration

Probing Electrode Heterogeneity Using Fourier-Transformed Alternating Current Voltammetry: Application to a Dual-Electrode Configuration

Dual-Plate Gold-Gold Microtrench Electrodes for Generator-Collector Voltammetry without Supporting Electrolyte

A Comprehensive Examination of Voltammetric Parameters in Fourier Transform Sine‐wave Voltammetry (FT‐SWV) Leading to Concentration Linearity and High Signal‐to‐background Ratio

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