Abstract
The oxygen evolution reaction (OER) in water electrolysis is a kinetically sluggish reaction that requires catalysts with high electrocatalytic activity. Cobalt oxide (CoO(x)) is among the best performing OER catalysts and has been reported to have "bulk activity" with active sites distributed within the material. Herein, we examined the distribution of OER activity over μg cm(-2) loaded CoO(x) deposited on anti-corrosive Ti substrate in 1 M KOH with and without various cations with chloride (X-Cl, X=Li, Na, K). Depth-resolved X-ray absorption spectroscopy and depth-profiling X-ray photoelectron spectroscopy were employed. In a thin sample with ~20 nm thickness, uniform oxidation was observed, but a thicker sample with ~80 nm thickness had active oxidized phases close to the surface and an unexpected inactive Co(0) phase concurrently occupying about three-quarters of the CoO(x) layer in the depth direction, which accounted for the mass activity loss. The formation of Co(0) in the bulk is attributed to the galvanic replacement reaction between CoO(x) and the metallic Ti substrate, which is not observed on the carbon substrate. Operando Raman spectroscopy demonstrated that the type of cations rather than Cl(-) impacts the OER performance likely due to their interaction with superoxo species.