Bond breaking electron transfer across a conducting nanowire(nanotube)/electrolyte solution interface: The role of electrical double layer effects

Abstract

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 DFT calculations. As example, the electronic transmission coefficients are calculated for Ag(111) 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.