Cr-doping promoted surface reconstruction of Ni₃N electrocatalysts toward efficient overall water splitting

Understanding and utilizing the dynamic changes of electrocatalysts under working conditions are important for advancing the sustainable hydrogen production. Here, we for the first time report that Cr-doping can promote the in situ reconstruction of a self-supported Ni₃N electrocatalyst (Cr-Ni₃N/NF) during oxygen and hydrogen evolution reactions (OER and HER), and therefore improve the electrocatalytic water splitting performance. As identified by in situ measurements and theoretical calculations, Cr-doping enhances OH^- adsorption during OER at anode and thereby boosts the transformation of Ni₃N pre-catalysts to defect-rich nickel oxyhydroxide (NiOOH) active species. Meanwhile, it facilitates the generation of Ni₃N/Ni(OH)₂ at cathodes due to effective H₂O activation, leading to the fast HER kinetics on the Ni₃N/Ni(OH)₂ interfaces. Notably, the optimal Cr-Ni₃N/NF displays good OER and HER performance in 1.0 M KOH electrolytes, with low overpotentials of 316 and 188 mV to achieve the current density of ± 100 mA cm^-2, respectively. Benefiting from its bi-functionality and self-supporting property, an alkaline electrolyzer equipped with Cr-Ni₃N/NF as both anode and cathode affords a small voltage of 1.72 V at 100 mA cm^-2, along with 100 h operation stability. Elucidating that Cr-doping can boost in situ reconfiguration and consequently the electrocatalytic activity, this work would shed new light on the rational design and synthesis of electrocatalysts via directional reconstructions.