Electron Delocalization in Ni–Co Active Pairs for Efficient and Robust Urea Electrooxidation

ABSTRACT Ni(OH) 2 is a promising urea oxidation reaction (UOR) catalyst, yet its performance is fundamentally limited by electron localization in Ni II that hinders the formation of active Ni III species. Herein, we overcome this limitation by constructing electron‐delocalized Ni–Co active pairs (Ni II+δ ‐O‐Co II+δ ) through Co doping of Ni(OH) 2 and integration with a CoNi alloy. This architecture exploits work‐function‐difference‐driven charge transfer to delocalize Ni II 3d electrons, thus accelerating the Ni II /Ni III transformation and achieving an ultralow UOR potential of 1.288 V RHE at 10 mA cm −2 , outperforming Ni II+δ ‐O‐Ni II+δ (1.333 V RHE ), Ni II ‐O‐Co II (1.349 V RHE ), and Ni II ‐O‐Ni II (1.365 V RHE ). Concurrently, the electron‐delocalized Ni–Co pairs with upshifted d‐band centers enhance N‐terminal urea adsorption and Ni/Co‐N charge transfer, which weakens N─H bonds and reduces the energy barrier of the rate‐determining step (CONH 2 NH 2 * → CONH 2 NH * ). The strengthened metal‐O bonding suppresses dissolution, achieving record stability for 2100 h across 10–500 mA cm −2 . Applied in a urea/urine electrolyzer, this catalyst enables energy‐saving hydrogen production (3.68/3.74 kW h m −3 at 100 mA cm −2 ), providing a dual‐purpose solution for sustainable energy and environmental remediation.