The performance of structurally and chemically well-defined Ni-free and Ni-modified single-crystalline Co3 O4 (1 1 1) thin-film electrodes in the oxygen reduction and evolution reactions (ORR and OER) was investigated in a combined surface science and electrochemistry approach. Pure and Ni-modified Co3 O4 (1 1 1) film electrodes were prepared and characterized under ultrahigh-vacuum conditions by scanning tunneling microscopy and X-ray photoelectron spectroscopy. Both Ni decoration (by post-deposition of Ni) and Ni doping (by simultaneous vapor deposition of Ni, Co, and O2 ) induced distinct differences in the base cyclic voltammograms in 0.5 m KOH at potentials higher than 0.7 V compared with Co3 O4 (1 1 1) electrodes. Also, all oxide film electrodes showed a higher overpotential for the ORR but a lower one for the OER than polycrystalline Pt. Ni modification significantly improved the ORR current densities by increasing the electrical conductivity, whereas the OER onset of approximately 1.47 VRHE (RHE: reversible hydrogen electrode) at 0.1 mA cm-2 was almost unchanged.
Keywords: electrochemistry; oxygen evolution reaction; oxygen reduction reaction; surface chemistry; thin films.
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