Industrial-current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm(-2).

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.