Industrial-Level Paired Electrosynthesis of Valuable Chemicals over a High-Performance Heterostructural Electrode

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@MoO_x 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 %, 304.4 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@MoO_x 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.