The bond breaking reduction of a peroxodisulphate anion at charged conducting cylinders of nanosize (which mimic metal wires or carbon tubes) in contact with an electrolyte solution is explored in the framework of a quantum mechanical theory and OFT calculations. As example, the electronic transmission coefficients are calculated for Ag(1 1 1) surface and silver nanowires of different size. The electron transfer is considered in adiabatic limit; current-voltage curves are computed for both conducting nanocylinders and a plain metal electrode, which is chosen as a reference system. It is argued that the electrical double layer effects play a crucial role and entail a noticeable rise of current at nanowires, as compared with a plain metal electrode. A "pit" on the model current-voltage dependencies was observed to disappear starting from a certain value of the radius of a nanocylinder. (C) 2011 Elsevier B.V. All rights reserved.