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

Abstract The electrocatalytic nitrate reduction (NO 3 RR) holds significance in both NH 3 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 NO 3 RR and water oxidation. Here, Cu 2 NCN with positive surface electrostatic potential V S (r) is applied as highly efficient NO 3 RR electrocatalysts to achieve industrial‐current and low‐voltage stable NH 3 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 NH 3 production rate of 97000 µg NH3 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 V S (r), promoting robust and asymmetric adsorption of NO 3 * on Cu 2 NCN 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 NH 3 synthesis.