Nano-ITIES array

Electrochemistry at nano-ITIES arrays (or ensembles depending on their periodicity) was pioneered by Dryfe et as summarized in an excellent 

The transfer of a probe ion across nano-ITIES arrays has been characterized voltammetrically. For instance, static IT voltammetry at the nano-ITIES array templated by a y-alumina membrane was used to determine membrane porosity. In this work, a nanoscale interface was formed at the orifice of each nanopore filled with the aqueous solution of a probe ion (tetraethylammonium, TEA ) in contact with the external organic solution (Fig. 17a). Potential sweep rates were chosen such that the mass transport of the probe ion during the forward potential sweep was controlled by the linear diffusion confined within nanopores (Fig. 17b). The resultant peak current based on TEA transfer depends on the total area of the nanoscale 

Linear diHusion of ion. diflusiod tieUs retained vbiitiinpvre 

Linear difAisicut field, individual fields overlap 

This reaction is thermodynamically spontaneous because the standard potential of the Pd couple is more positive than that of the ferrocene couple. The equilibrium position and rate of the heterogeneous ET reaction at the ITIES, however, depends on the phase boundary potential, which can be controlled externally for electrodeposition or by a common ion in the aqueous and organic phases for electroless deposition. Similarly, Pt NPs were deposited at nano-ITIES arrays. A more detailed discussion of particle deposition at the ITIES is given in the next section. 

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Fig. 17 Schematic of (a) the array of nano-ITIES and the time-dependent growth of diffusion layers in the inner solution from (b) linear to (c) radial and back to (d) linear in form. Adapted with permission from ref 84. Copyright 2003 American Chemical Society.

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