Processes at electrode surfaces strongly depend on the nature of the solid | liquid (electrolyte) interaction. This is also the case for processes at solid | liquid | liquid line interfaces and demonstrated here for the case of electrochemical processes at electrode | organic liquid | aqueous electrolyte triple phase boundaries.Experimental data are obtained at metal, carbon, and ceramic electrodes and for porphyrinato metal complexes immobilised in water-immiscible organic liquids in contact with an aqueous electrolyte [1]. Voltammetric data are discussed and the porosity of surfaces identified as a key parameter for optimising electrochemically driven ion transfer processes. Both the transfer of inert ions and facilitated ion transfer are considered.

[1] F. Marken, K. J. McKenzie, G. Shul, M. Opallo, Faraday Discussions, 129 (2005) 219.