Abstract
It has been shown previously that conventional voltammetric theories may become inapplicable at electrodes of nanometer scale due to enhanced effects of the diffuse double layer on the interfacial charge transport and transfer processes (Anal. Chem. 1993, 65, 3343; J. Phys. Chem. B 2006, 110, 3262). As well as the diffuse double layer effects, we show in present study that the voltammetric responses of nanometer-sized electrodes would differ from the macroscopic electrodes due to significant edge effects of dielectric screening and electron tunneling if the electrode has planar geometries. These nanoedge effects arise because of the comparable size of the electrode with the dipole molecules and the effective electron tunneling distance. Models for these nanoedge effects are developed and combined with Poisson−Nernst−Planck theory and Marcus electron-transfer theory to describe the voltammetric characteristics of nanometer-sized disk electrodes. Marcus theory instead of Butler−Volmer theory is used to desc...
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