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Electrochemical nitrate reduction reaction (NO3RR) is a promising means for generating the energy carrier ammonia. Herein, we report the synthesis of heterostructure copper-nickel phosphide electrocatalysts via a simple vapor-phase hydrothermal method. The resultant catalysts were evaluated for electrocatalytic nitrate reduction to ammonia (NH3) in three-type electrochemical reactors. In detail, the regulation mechanism of the heterogeneous Cu3P-Ni2P/CP-x for NO3RR performance was systematically studied through the H-type cell, rotating disk electrode setup, and membrane-electrode-assemblies (MEA) electrolyzer. As a result, the Cu3P-Ni2P/CP-0.5 displays the practicability in an MEA system with an anion exchange membrane, affording the largest ammonia yield rate (RNH3) of 1.9 mmol·h−1·cm−2, exceeding most of the electrocatalytic nitrate reduction electrocatalysts reported to date. The theoretical calculations and in-situ spectroscopy characterizations uncover that the formed heterointerface in Cu3P-Ni2P/CP is beneficial for promoting nitrate adsorption, activation, and conversion to ammonia through the successive hydrodeoxygenation pathway.
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