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Herein, the effect of the alkali cation (Li+ , Na+ , K+ , and Cs+ ) in alkaline electrolytes with and without Fe impurities is investigated for enhancing the activity of nickel oxyhydroxide (NiOOH) for the oxygen evolution reaction (OER). Cyclic voltammograms show that Fe impurities have a significant catalytic effect on OER activity; however, both under purified and unpurified conditions, the trend in OER activity is Cs+ > Na+ > K+ > Li+ , suggesting an intrinsic cation effect of the OER activity on Fe-free Ni oxyhydroxide. In situ surface enhanced Raman spectroscopy (SERS), shows this cation dependence is related to the formation of superoxo OER intermediate (NiOO- ). The electrochemically active surface area, evaluated by electrochemical impedance spectroscopy (EIS), is not influenced significantly by the cation. We postulate that the cations interact with the Ni-OO- species leading to the formation of NiOO- -M+ species that is stabilized better by bigger cations (Cs+ ). This species would then act as the precursor to O2 evolution, explaining the higher activity.
Garcia et al. (Fri,) studied this question.