Journal
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
Volume 633, Issue 1, Pages 235-239Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2009.06.003
Keywords
Time delay; Random walk simulation; Diffusion; Electrochemical detection
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For a sphere electrode enclosed in finite-volume electrolyte, the measured current will deviate from the result predicted by the semi-infinite diffusion theory after some time. By random-walk simulation, we compared this time to the one needed for diffusion layer to reach electrolyte boundary, and revealed a clear signal delay of electrochemical current. Further we presented a quantitative description of this delay time. The simulation results suggested that the semi-infinite diffusion theory can even be applied when the theoretical diffusion layer grows to 1.28 electrolyte thicknesses, with an accuracy better than 0.5%. We attributed this time delay to the molecules' finite propagation velocity. Finally, we discussed how this delay can influence and facilitate the following electrochemical detection towards the nanometer and single-cell scale. (C) 2009 Elsevier B.V. All rights reserved.
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