Enhancement of the electrochemical reduction of oxygen at platinum by nickel underpotential deposition

Abstract

Polycrystalline Pt electrode was modified by underpotential deposition (upd) of nickel. The modification was performed by potential cycling in phosphate buffer pH 7. 0 containing NiSO4, in which hydrogen and nickel upd processes were well separated. The maximum Ni upd coverage was found to be 0.3. Oxygen reduction was studied at bare and nickel upd-modified Pt. It was found that the reaction rate increased with increasing Ni upd coverage. At theta(Ni)=0.3, the current density was a factor of 2 higher compared to bare Pt (at the potential of 0.85 V). The capacitance of the electrode interface was determined in potential-relaxation experiments following interruption of the polarization current. It was found that the pseudocapacitance owing to a coverage by the adsorbed reaction intermediates was higher on the Ni-modified Pt surface than on bare Pt, which resulted in higher reaction rate. The influence of Ni adatoms on the surface coverage by the reaction intermediates was attributed to the inhibition of OH adsorption on Pt by OH ligands attached on neighboring Ni atoms.