Unveiling Electrochemical Urea Synthesis by Co‐Activation of CO₂ and N₂ with Mott–Schottky Heterostructure Catalysts

Electrocatalytic C-N bond coupling to convert CO₂ and N₂ molecules into urea under ambient conditions is a promising alternative to harsh industrial processes. However, the adsorption and activation of inert gas molecules and then the driving of the C-N coupling reaction is energetically challenging. Herein, novel Mott-Schottky Bi-BiVO₄ heterostructures are described that realize a remarkable urea yield rate of 5.91 mmol h^-1 g^-1 and a Faradaic efficiency of 12.55 % at -0.4 V vs. RHE. Comprehensive analysis confirms the emerging space-charge region in the heterostructure interface not only facilitates the targeted adsorption and activation of CO₂ and N₂ molecules on the generated local nucleophilic and electrophilic regions, but also effectively suppresses CO poisoning and the formation of endothermic *NNH intermediates. This guarantees the desired exothermic coupling of *N=N* intermediates and generated CO to form the urea precursor, *NCON*.