Paired electrosynthetic technology is of significance to realize the co-production of high-added value chemicals. However, exploiting efficient bifunctional electrocatalyst of the concurrent electrocatalysis to achieve the industrial-level performance is still challenging. Herein, an amorphous Co2P@MoOx heterostructure is rationally designed by in-situ electrodeposition strategy, which is acted as excellent bifunctional catalysts for the electrocatalytic nitrite reduction reaction (NO2RR) and glycerol oxidation reaction (GOR). The membrane-electrode assembly (MEA) electrolyzer realizes a low voltage of 1.30 V, robust stability over 200 h at 100 mA cm-2, high Faraday efficiencies and yield of NH3 (above 95%, 49.7 mg h-1 cm-2) and formate (above 95%, 152.3 mg h-1 cm-2) at industrial-level current density of 500 mA cm-2. In-situ spectroscopy studies have shown that high-valence CoOOH is the main active material of GOR, and the main catalytic conversion pathway of NO2RR involves key *NH2OH reaction intermediates. In addition, theoretical calculations confirm that the Co2P@MoOx heterostructure has strong interfacial electronic interaction and optimized reaction energy barriers, which endows its intrinsically high electrocatalytic activity for the co-electrosynthesis of NH3 and formate.
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