科研之友
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摘要
Recent theoretical and experimental studies revealed strong effects of the electrical double layer (EDL) on mass transfer at nanometer-sized electrodes and in electrochemical nanogaps. Although the EDL effect is much stronger in weakly supported media, it can significantly influence the kinetics of electron-transfer processes involving multicharged ionic redox species, even at high concentrations of supporting electrolyte. We measured the kinetics of Fe(CN)(6)(4-) oxidation in 1 M KCl solution at the Pt nanoelectrode used as a tip in the scanning electrochemical microscope. The apparent standard rate constant values extracted from tip voltammograms without double-layer correction increased markedly with the decreasing separation distance between the tip and substrate electrodes. The same steady-state voltammograms were fitted to the theory including the EDL effect and yielded the rate constant essentially independent of the separation distance.
- 出版日期2017-4-6
