Activating Lattice Oxygen in Layered Lithium Oxides through Cation Vacancies for Enhanced Urea Electrolysis

Despite the fact that high-valent nickel-based oxides exhibit promising catalytic activity for the urea oxidation reaction (UOR), the fundamental questions concerning the origin of the high performance and the structure-activity correlations remain to be elucidated. Here, we unveil the underlying enhanced mechanism of UOR by employing a series of prepared cation-vacancy controllable LiNiO₂ (LNO) model catalysts. Impressively, the optimized layered LNO-2 exhibits an extremely low overpotential at 10 mA cm^-2 along with excellent stability after the 160 h test. Operando characterisations combined with the theoretical analysis reveal the activated lattice oxygen in layered LiNiO₂ with moderate cation vacancies triggers charge disproportion of the Ni site to form Ni⁴⁺ species, facilitating deprotonation in a lattice oxygen involved catalytic process.