In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen

An in situ Raman spectroscopic investigation has been carried out to identify the composition of the active phase present on the surface of nickel electrodes used for the electrochemical evolution of oxygen. The electrolyte in all cases was 0.1 M KOH. A freshly polished Ni electrode oxidized upon immersion in the electrolyte and at potentials approaching the evolution of oxygen developed a wlayer of gamma-NiOOH. Electrochemical cycling of this film transformed it into beta-NiOOH, which was observed to be three times more active than gamma-NiOOH. The higher activity of beta-NiOOH is attributed to an unidentified Ni oxide formed at a potential above 0.52 V (vs Hg/HgO reference). We have also observed that a submonolayer of Ni oxide deposited on Au exhibits a turnover frequency (TOF) for oxygen evolution that is an order of magnitude higher than that for a freshly prepared gamma-NiOOH surface and more than 2-fold higher than that for a beta-NiOOH surface. By contrast, a similar film deposited on Pd exhibits a TOF that is similar to that of bulk gamma-NiOOH. It is proposed that the high activity of submonolayer deposits of Ni oxide on Au is due to charge transfer from the oxide to the highly electronegative Au, leading to the possible formation of a mixed Ni/Au surface oxide.