Engineering d–p Orbital Hybridization in Mo‐O Species of Medium‐Entropy Metal Oxides as Highly Active and Stable Electrocatalysts toward Ampere‐Level Water/Seawater Splitting

Abstract Optimizing the electronic structure of electrocatalysts is of particular importance to enhance the intrinsic activity of active sites in water/seawater. Herein, a series of medium‐entropy metal oxides of X(NiMo)O 2 /NF (X = Mn, Fe, Co, Cu and Zn) is designed via a rapid carbothermal shocking method. Among them, the optimized medium‐entropy metal oxide (FeNiMo)O 2 /NF delivered remarkable HER performance, where the overpotentials as low as 110 and 141 mV are realized at 1000 mA cm −2 (@60 °C) in water and seawater. Meanwhile, medium‐entropy metal oxide (FeNiMo)O 2 /NF only required overpotentials of as low as 330 and 380 mV to drive 1000 mA cm −2 for OER in water and seawater (@60 °C). Theoretical calculations showed that the multiple‐metal synergistic effect in medium‐entropy metal oxides can effectively enhance the d–p orbital hybridization of Mo─O bond, reduce the energy barrier of H * adsorbed at the Mo sites. Meanwhile, Fe sites in medium‐entropy metal oxide can act as the real OER active center, resulting in a good bifunctional activity. In all, this work provides a feasible strategy for the development of highly active and stable medium‐entropy metal oxide electrocatalysts for ampere‐level water/seawater splitting.