Nanoelectrodes, electrical transport

What happens when the dimensions are furthermore reduced Initially, an enhanced diffusive mass transport would be expected. That is true, until the critical dimension is comparable to the thickness of the electrical double layer or the molecular size (a few nanometers) [7,8]. In this case, diffusive mass transport occurs mainly across the electrical double layer where the characteristics (electrical field, ion solvent interaction, viscosity, density, etc.) are different from those of the bulk solution. An important change is that the assumption of electroneutrality and lack of electromigration mass transport is not appropriate, regardless of the electrolyte concentration [9]. Therefore, there are subtle differences between the microelectrodic and nanoelectrodic behaviour. 

For electrodes with dimensions in the tens of nm range, the diffusion layer is decreased to achieve dimensions comparable with the thickness of the electrical double layer. Electrostatic forces within the double layer can accelerate the flux of oppositely charged redox species, so generating the conditions for a further enhancement of the mass transport to the nanoelectrodes surface. Dickinson and Compton presented numerical solution of the Poisson-Boltzman equation, for... 

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