Nonergodicity in nanoscale electrodes

Literature Information

Publication Date 2012-10-01
DOI 10.1039/C2CP42838E
Impact Factor 3.676
Authors

Diego Krapf


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Abstract

The response of nanoscale electrodes displays deviations from conventional voltammetry theory that include a reduction in the limiting current and enhanced current fluctuations. We study the power spectra of these fluctuations in well characterized conical electrodes with radii between 2 and 10 nm. The fluctuations are found to display non-trivial power laws. We propose a model based on reversible adsorption of the redox species onto the nanoelectrode. This model is consistent with the non-stationary character of both the limiting current and the adsorption of molecules onto metal electrodes. Our model predicts the electrochemical reaction is nonergodic and sets fundamental limits on the sensitivity of uncoated nanoelectrodes.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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