Abstract Durable and efficient Fe‐based electrocatalysts in alkaline freshwater/seawater electrolysis is highly desirable but persists a significant challenge. Herein, we report a durable and robust heterogenous nitrogen‐doped FeMoO 4 /Mo 2 N rod‐shaped catalyst on nickel foam (denoted NF@FMO/MN) affording hydrogen evolution reaction (HER) low overpotentials of 23/29 mV@10 mA cm −2 and 112/159 mV@100 mA cm −2 in both alkaline freshwater/seawater electrolytes, respectively. These results are significantly superior to the pristine FeMoO 4 catalyst. Theoretical calculations consistently reveals that the combination of N‐FeMoO 4 and Mo 2 N effectively reduces water activation energy barrier, modulates the sluggish water‐dissociation kinetics and accelerates the hydrogen adsorption process for efficient HER. The enhanced HER performance of the as‐designed NF@FMO/MN catalyst is attributed to the in situ hetero‐interfacial engineering between N‐doped FeMoO 4 and Mo 2 N. This present work nurtures the progress of FeMo‐based electrocatalysts in alkaline freshwater/seawater electrolysis.
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