Microholes micro

Most electrochemical studies at the micro-ITIES were focused on ion transfer processes. Simple ion transfer reactions at the micropipette are characterized by an asymmetrical diffusion field. The transfer of ions out of the pipette (ejection) is controlled by essentially linear diffusion inside its narrow shaft, whereas the transfer into the pipette (injection) produces a spherical diffusion field in the external solution. In contrast, the diffusion field at a microhole-supported ITIES is approximately symmetrical. Thus, the theoretical descriptions for these two types of micro-ITIES are somewhat different. 

Quinn et al. studied ET at micro-ITIES supported by micropipettes or microholes [16]. The studied systems involved ferri/ferrocyanide redox couple in aqueous phase and ferrocene, dimethylferrocene, or TCNQ in either DCE or o-nitrophenyl octyl ether. Sigmoidal, steady-state voltammograms were obtained for ET at the water-DCE interface supported at a micropipette. The semilogarithmic plot of E versus log[(/(j — /)//] was... 

The voltammograms at the microhole-supported ITIES were analyzed using the Tomes criterion [34], which predicts ii3/4 — iii/4l = 56.4/n mV (where n is the number of electrons transferred and E- i and 1/4 refer to the three-quarter and one-quarter potentials, respectively) for a reversible ET reaction. An attempt was made to use the deviations from the reversible behavior to estimate kinetic parameters using the method previously developed for UMEs [21,27]. However, the shape of measured voltammograms was imperfect, and the slope of the semilogarithmic plot observed was much lower than expected from the theory. It was concluded that voltammetry at micro-ITIES is not suitable for ET kinetic measurements because of insufficient accuracy and repeatability [16]. Those experiments may have been affected by reactions involving the supporting electrolytes, ion transfers, and interfacial precipitation. It is also possible that the data was at variance with the Butler-Volmer model because the overall reaction rate was only weakly potential-dependent [35] and/or limited by the precursor complex formation at the interface [33b]. 

Micro-spark and stray-current affected zone (MSAZ) in machined microhole [11],... 

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