Unveiling the Electrooxidation of Urea: Intramolecular Coupling of the N−N Bond

Abstract The nitrogenous nucleophile electrooxidation reaction (NOR) plays a vital role in the degradation and transformation of available nitrogen. Focusing on the NOR mediated by the β‐Ni(OH) 2 electrode, we decipher the transformation mechanism of the nitrogenous nucleophile. For the two‐step NOR, proton‐coupled electron transfer (PCET) is the bridge between electrocatalytic dehydrogenation from β‐Ni(OH) 2 to β‐Ni(OH)O, and the spontaneous nucleophile dehydrogenative oxidation reaction. This theory can give a good explanation for hydrazine and primary amine oxidation reactions, but is insufficient for the urea oxidation reaction (UOR). Through operando tracing of bond rupture and formation processes during…