Deciphering and Suppressing Over‐Oxidized Nitrogen in Nickel‐Catalyzed Urea Electrolysis

Abstract

Urea electrolysis is a prospective technology for simultaneous H₂ production and nitrogen suppression in the process of water being used for energy production. Its sustainability is currently founded on innocuous N₂ products; however, we discovered that prevalent nickel-based catalysts could generally over-oxidize urea into NO₂ ^- products with ≈80 % Faradaic efficiencies, posing potential secondary hazards to the environment. Trace amounts of over-oxidized NO₃ ^- and N₂ O were also detected. Using ¹⁵ N isotopes and urea analogues, we derived a nitrogen-fate network involving a NO₂ ^- -formation pathway via OH^- -assisted C-N cleavage and two N₂ -formation pathways via intra- and intermolecular coupling. DFT calculations confirmed that C-N cleavage is energetically more favorable. Inspired by the mechanism, a polyaniline-coating strategy was developed to locally enrich urea for increasing N₂ production by a factor of two. These findings provide complementary insights into the nitrogen fate in water-energy nexus systems.