Kinetics of electron transfer to organic molecules at solid electrodes in organic media

Amatore, Christian; Savéant, Jean Michel; Tessier, D.

doi:10.1016/s0022-0728(83)80111-9

Cited by 104 publications

(59 citation statements)

References 17 publications

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“…The reactive distance is sensitive to the sizes of both the reactant and the supporting electrolyte ions. This last effect has been evidenced in organic solvent with nitro compounds and with others several examples [38,50]. In our situation, if we cannot reject that a distance effect be responsible for subtle variation when passing from ACN to the RTILs, for a given cation, it seems unlikely that the relation between the size of the reactant and the reactive distance was greatly modify when changing the solvent type especially taking into account that similar cations are used in the supporting electrolyte (Bu 4 …”

Section: Resultsmentioning

confidence: 52%

“…On the contrary, the electron transfer kinetics for the aliphatic (6) remains almost unchanged in the ionic liquids taking into account the experimental error on the k s determinations. As discussed before [38,40,50], a possible factor for controlling the heterogeneous electron-transfer kinetics is the size of the electrolyte cation that modifies the approach distance of the molecule to the electrode at which the electron transfer occurs. The reactive distance is sensitive to the sizes of both the reactant and the supporting electrolyte ions.…”

Section: Resultsmentioning

confidence: 99%

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Heterogeneous electron-transfer kinetics of nitro compounds in room-temperature ionic liquids

Lagrost

Preda

Volanschi

et al. 2005

Journal of Electroanalytical Chemistry

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Section: Resultsmentioning

confidence: 52%

Section: Resultsmentioning

confidence: 99%

Heterogeneous electron-transfer kinetics of nitro compounds in room-temperature ionic liquids

Lagrost

Preda

Volanschi

et al. 2005

Journal of Electroanalytical Chemistry

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“…We also suppose that a steady‐state situation occurs due to natural convection, and we assume that the extent of the convection‐free layer has an average value, namely, 200 μm . The response of the microelectrode array was simulated taking into account the symmetry of the ordered array; hence, only a single unit cell (or diffusion domain) was simulated (shown in Figure b) . Although in the arrays used in our previous experiments the unit cells had a square shape (see Figure a), in our simulations we considered a cylindrical unit cell with radius r c (its value being adjustable in order to yield the same surface area as for the corresponding square or hexagonal unit cell).…”

Section: Resultsmentioning

confidence: 99%

Theory of Microwell Arrays Performing as Generators–Collectors Based on a Single Bipolar Plane Electrode

et al. 2015

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Electroanalytical arrays of microwells with increased sensitivity and virtual immunity to interferents have been previously reported by us. Such arrays were designed to be operated in a classical generator–collector mode but exhibited also similar properties when their common planar collector was left floating. This evidenced that the unbiased collector acted as a bipolar electrode. In this work, a theory is elaborated to investigate in great detail the generality of this phenomenon and its limits. This establishes that if the analyte pertains to a redox couple with relatively fast electron rate constants, the bipolar collector results to be almost as efficient as when biased, thus suppressing the need for a bi‐potentiostat with obvious gain for analytical applications. Conversely, if the analyte rate constant of electron transfer is small, efficient operation in a bipolar mode remains feasible but requires a drastic decrease of the microwell density in the array.

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“…Rigorous mathematical solutions of diffusion at statistical arrays are impossible to obtain. The general solutions of ordered arrays are mostly used for random arrays with a statistical correction 61–65. For ordered arrays, and to a first approximation for the random array we developed, where the electrodes are operated at an identical potential, the total response of the array depends on the size of the electrodes in the array and the interelectrode distance d which determines the thickness of the diffusion layer developing at each electrode of the array.…”

Section: Electrochemical Characterization Of the Optoelectrochemicmentioning

confidence: 99%

The Use of Optical Fiber Bundles Combined with Electrochemistry for Chemical Imaging

Szunerits

Walt

2003

ChemPhysChem

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The present Review describes the progress made in using imaging optical fiber bundles for fluorescence and electrochemical-initiated chemiluminescence imaging. A novel optoelectrochemical microring array has been fabricated and demonstrated for concurrent electrochemical and optical measurements. The device comprises optical fibers coated with gold via electroless gold deposition and assembled in a random array format. The design yielded an array of approximately 200 micro-ring electrodes, where interdiffusional problems were minimized. The inner diameter of the ring electrode is fixed by the diameter of the individual optical fibers (25 mm), while the outer radius is determined by the thickness of the deposited gold. While all the fibers are optically addressable, they are not all electrochemically addressable. The resolution of this device is in the tens of micrometers range, determined by the diameter of the optical fiber (25 mm) and by the spacing between each electrically connected fiber. For the purpose of having wellbehaved microelectrode characteristics, this spacing was designed to be larger than 60 mm. The array was characterized using ferrocyanide in aqueous solution as a model electroactive species to demonstrate that this microelectrode array format exhibits steady-state currents at short response times. This device has potential application to be used as an optoelectronic sensor, especially for the electrolytic generation and transmission of electrochemiluminescence, and was used to demonstrate that electrochemically generated luminescent products can be detected with the fiber assembly.

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Kinetics of electron transfer to organic molecules at solid electrodes in organic media

Cited by 104 publications

References 17 publications

Heterogeneous electron-transfer kinetics of nitro compounds in room-temperature ionic liquids

Heterogeneous electron-transfer kinetics of nitro compounds in room-temperature ionic liquids

Theory of Microwell Arrays Performing as Generators–Collectors Based on a Single Bipolar Plane Electrode

The Use of Optical Fiber Bundles Combined with Electrochemistry for Chemical Imaging

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