Unraveling Oxyanion Effects on Oxygen Evolution Electrocatalysis of Nickel Hydr(oxy)oxides: The Critical Role of Fe Impurities

Electrolyte modulation can enhance the performance of electrocatalysts for the oxygen evolution reaction (OER) by tailoring the electrocatalyst-electrolyte interface, but the role of anion additives remains controversial. Herein, we report our findings on unraveling the effects of oxyanions (NO₃^-, SO₄^2-, and PO₄^3-) and identifying Fe impurities as the key factor driving OER activity enhancement in Ni hydr(oxy)oxide model catalysts. Fe impurities, introduced via oxyanion salts, significantly enhance OER activity, while oxyanions themselves have minimal direct impact when Fe ions are removed. Our results, including <i>operando</i> Raman spectroscopy, reveal that Fe enhances Ni reducibility/redox reversibility. X-ray absorption spectroscopy and density functional theory calculations indicate that Fe preferentially adsorbs on Ni surface sites with higher deprotonation energy. These findings reveal the critical role of surface-adsorbed Fe in modulating Ni hydr(oxy)oxide activity and highlight overlooked impurity effects in electrocatalysis when studying additive effects in electrolyte modulation.