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.

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/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/NF delivered remarkable HER performance, where the overpotentials as low as 110 and 141 mV are realized at 1000 mA cm (@60 °C) in water and seawater. Meanwhile, medium-entropy metal oxide (FeNiMo)O/NF only required overpotentials of as low as 330 and 380 mV to drive 1000 mA cm 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.