Nickel-Based Bicarbonates as Bifunctional Catalysts for Oxygen Evolution and Reduction Reaction in Alkaline Media

Oxygen electrocatalysis, including the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), is one of the most important electrochemical processes for sustainable energy conversion and storage technologies. Herein, nickel-based bicarbonates are, for the first time, developed as catalysts for oxygen electrocatalysis, and demonstrate superior electrocatalytic performance in alkaline media. Iron doping can significantly tune the real valence of nickel ions, and consequently tailor the electrocatalytic ability of bicarbonates. Among the nickel-based bicarbonates, Ni_0.9Fe_0.1(HCO₃)₂ exhibits the highest bifunctional catalytic activity, with a potential difference of 0.86 V between the OER potential at a current density of 10 mA cm⁻² and the ORR potential at a current density of −1 mA cm⁻², which outperforms most of the reported precious-metal-free catalysts. The present work provides new insights into exploring efficient catalysts for oxygen electrocatalysis, and it suggests that, in addition to the extensively studied transition metal hydroxides and oxides, bicarbonates and carbonates also show great potential as precious metal-free catalysts.