A Lattice‐Oxygen‐Involved Reaction Pathway to Boost Urea Oxidation

The electrocatalytic urea oxidation reaction (UOR) provides more economic electrons than water oxidation for various renewable energy-related systems owing to its lower thermodynamic barriers. However, it is limited by sluggish reaction kinetics, especially by CO₂ desorption steps, masking its energetic advantage compared with water oxidation. Now, a lattice-oxygen-involved UOR mechanism on Ni⁴⁺ active sites is reported that has significantly faster reaction kinetics than the conventional UOR mechanisms. Combined DFT, ¹⁸ O isotope-labeling mass spectrometry, and in situ IR spectroscopy show that lattice oxygen is directly involved in transforming *CO to CO₂ and accelerating the UOR rate. The resultant Ni⁴⁺ catalyst on a glassy carbon electrode exhibits a high current density (264 mA cm^-2 at 1.6 V versus RHE), outperforming the state-of-the-art catalysts, and the turnover frequency of Ni⁴⁺ active sites towards UOR is 5 times higher than that of Ni³⁺ active sites.