The rational design of highly active and stable electrocatalysts toward the hydrogen evolution reaction (HER) is highly desirable but challenging in seawater electrolysis. Herein we propose a strategy of boron-doped three-dimensional NiP-MoO heterostructure microrod arrays that exhibit excellent catalytic activity for hydrogen evolution in both alkaline freshwater and seawater electrolytes. The incorporation of boron into NiP-MoO heterostructure microrod arrays could modulate the electronic properties, thereby accelerating the HER. Consequently, the B-NiP-MoO heterostructure microrod array electrocatalyst exhibits a superior catalyst activity for HER with low overpotentials of 155, 155, and 157 mV at a current density of 500 mA cm in 1 M KOH, 1 M KOH + NaCl, and 1 M KOH + seawater, respectively. It also exhibits exceptional performance for HER in natural seawater with a low overpotential of 248 mV at 10 mA cm and a long-lasting lifetime of over 100 h.
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