High-sensitivity spectroelectrochemistry based on electrochemical modulation of an absorbing analyte

Jan, Chwu Ching.; Lavine, Barry K.; McCreery, Richard L.

doi:10.1021/ac00280a040

Cited by 29 publications

(15 citation statements)

References 25 publications

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“…A particular segment of the beam emerging from the cell will have sampled a range of distances, and the resolution will be degraded. This effect has been studied in detail (24), and an expression for lateral displacement by a linear concentration profile is given by eq 2 where a = lateral The imaging method presented here shares the parallel geometry with the diffractive technique we have reported earlier (39)(40)(41), but the two methods differ in how the transmitted light is analyzed. For the diffractive method, it was shown that light diffracted at higher angles passed closer to the electrode surface, and this property was exploited to limit the absorbance measurement to regions within about 10 pm of the electrode surface.…”

Section: Discussionmentioning

confidence: 99%

High-resolution spatially resolved visible absorption spectrometry of the electrochemical diffusion layer

Jan¹,

McCreery²

1986

Anal. Chem.

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M through 1 X lo4 M. The slope of the calibration curve was 0.506 f 0.035 pA/pM. The minimum detectable difference between the background and sample solution estimated by paired measurements (5) was 0.025 pM, which is over an order of magnitude lower than in the dc polarographic method (1 7).A voltammogram of a 5.0 X lo4 M Ti(IV) solution is presented in Figure 10. ACKNOWLEDGMENTThe authors thank Janet Osteryoung for helpful discussion.(1) Brdicka, R.; Wlesner, K.Concentration vs. distance profiles are fundamental to a variety of electrochemical processes but have not been observed previously at resolutions better than 25 pm. I n the present work, a collimated He-Ne laser beam was passed parallel to a planar electrode surface and then magntfied and imaged onto an array detector. Each pixel of the detector

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Section: Discussionmentioning

confidence: 99%

High-resolution spatially resolved visible absorption spectrometry of the electrochemical diffusion layer

Jan¹,

McCreery²

1986

Anal. Chem.

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“…For greater sensitivity of surface species, such as the detection of very low concentrations of adsorbed species on the electrode, the potential of the electrode has been modulated [40,60,162,163]. The sensitivities of the various techniques have been compared [162]. A recent paper addresses the theoretical background [164].…”

Section: Reflection From Electrodes and Liquid-liquid Interfacesmentioning

confidence: 99%

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

Crayston

2003

Encyclopedia of Electrochemistry

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The sections in this article are Introduction and Principles Introductory Remarks Theory and Techniques: Steady State Measurement Cell Transmission for a Simple Electron Transfer Reaction: Determination of E and n Effect of Follow‐up Reactions in OTTLE Cells Theory and Techniques: Kinetic Measurements Chronoabsorptometry Instrumentation for Chronoabsorptometry Slow Heterogeneous Kinetics Effect of Follow‐up Reactions Derivative Cyclic Voltabsorptometry ( DCVA ) Galvanostatic Conditions Adsorption Cell Geometries, Design, Techniques, and Instrumentation General Considerations Transmission under Thin‐layer Conditions: OTTLEs and Flow‐cells Variations on and Alternatives to the Basic OTTLE Design OTTLE Cells Intended for Both UV ‐visible and FTIR Use OTTLE Cell Electrochemical and Spectroscopic Response Semi‐infinite Cells: Optically Transparent Electrodes ( OTEs ) Reflection from Electrodes and Liquid–Liquid Interfaces Glancing Incidence Reflection, Near‐parallel or Parallel Reflection, and Diffraction Liquid–Liquid Interface and Attenuated Total Reflection Long Optical Path‐length Thin‐layer Cell ( LOPTLC ) Forced Convection, RDE and Channel Flow UV ‐vis Combined with Other Spectroscopic Techniques Applications Solution Studies of Inorganic Species Solution Studies of Organic Species Molten Salts Spectroelectrochemistry Studies of Species of Biological Interest Inorganic Thin Films and Modified Electrodes Conducting Polymers and Oligomer Models Conclusions

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“…6,7 Previously, the implementation of spectroelectrochemistry based on the measurement of the absorbance, by the dilute species, of a monochromatic light diffracted by the working electrode, allowed determination of the local concentration of the absorbing species in the diffusion layer close to the electrode. 8 But despite the very good detection limit of this technique around 10 -8 M, concentration is measured only in specific conditions for which the absorbance of light by the species is linearly related to concentration in the Beer's law fashion. Moreover, the technique requires a colored main species and a colorless environment for this species.…”

Section: Introductionmentioning

confidence: 99%

An Electrodeposition Process Followed by X-ray Microscopy

Rondot¹,

Aaboubi²,

Cazaux³

et al. 1997

J. Phys. Chem. B

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Time-dependent X-ray microscopy has been applied for the first time to follow an electrodeposition process: that of copper on a glassy carbon electrode. From a series of X-ray microradiographs taken every 20 s it is possible not only to measure directly the increasing thickness of the coating but also to evaluate the copper sulfate concentration profile in the electrolyte at the corresponding instants of acquisition. When the electrodeposition conditions lead to ramified growth close to coating/electrolyte interface, local variations of the ionic concentration are observed as a function of time and of coordinates. The lateral resolution is in the 10−20 μm range and relative concentration changes of few percent are easily detected.

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High-sensitivity spectroelectrochemistry based on electrochemical modulation of an absorbing analyte

Cited by 29 publications

References 25 publications

High-resolution spatially resolved visible absorption spectrometry of the electrochemical diffusion layer

High-resolution spatially resolved visible absorption spectrometry of the electrochemical diffusion layer

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

An Electrodeposition Process Followed by X-ray Microscopy

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