Industrial‐current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm−2

The electrocatalytic nitrate reduction (NO3RR) holds significance in both NH3 synthesis and nitrate contamination remediation. However, achieving industrial‐scale current and high stability in membrane electrode assembly (MEA) electrolyzer remains challenging due to inherent high full‐cell voltage for sluggish NO3RR and water oxidation. Here, Cu2NCN with positive surface electrostatic potential VS(r) is applied as highly efficient NO3RR electrocatalysts to achieve industrial‐current and low‐voltage stable NH3 production in MEA electrolyzer with coupled anodic glycerol oxidation. This paired electro‐refinery (PER) system reaches 4000 mA cm−2 at 2.52 V and remains stable at industrial‐level 1000 mA cm−2 for 100 h with the NH3 production rate of 97000 µgNH3 h−1 cm−2 and a Faradaic efficiency of 83%. Theoretical calculations elucidate that the asymmetric and electron‐withdrawing [N−C≡N] units enhance polarization and VS(r), promoting robust and asymmetric adsorption of NO3* on Cu2NCN to facilitate O−N bond dissociation. A comprehensive techno‐economic analysis demonstrates the profitability and commercial viability of this coupled system. Our work opens a new avenue and marks a significant advancement in MEA systems for industrial NH3 synthesis.