Electrosynthesis of hydrogen straightforwardly from seawater represents a potential solution towards carbon-neutral economy. However, with the sluggish oxygen evolution reaction (OER) at anode, the sustainable and cost-effective application is greatly hindered by extra energy consumption and serious chlorine chemistry in seawater. Herein, based on the advanced hydrazine-assisted electrolysis strategy, we reported a trifunctional Fe, P dual-doping NiMoO4 nanorods with a hollow structure for highly active hydrogen evolution reaction (HER) (23 mV @ 10 mA cm−2) and OER (213 mV @ 10 mA cm−2) activity, which also significantly decreased the cell voltage (activity variation for ∼1.40 V) in two-electrode system by replacing OER with thermodynamically beneficial hydrazine oxidation reaction (HzOR). Notably, a record low electricity expense of 2.3 kW h m−3 was obtained among commercial reactor in alkaline seawater/0.5 M N2H4. Meanwhile, the corrosion resistance of catalyst allows stable catalytic performance in seawater without any ClO- generation. Density functional theory calculations showed that Fe/P co-doping effectively endowed optimized electronic structure and modulated d-band centre for intermediates adsorption/desorption.
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