Rectifying Heterointerface Facilitated C‐N Coupling Dynamics Enables Efficient Urea Electrosynthesis Under Ultralow Potentials

Electrocatalytic C‐N coupling for urea synthesis from carbon dioxide (CO2) and nitrate (NO3‐) offers a sustainable alternative to the traditional Bosch‐Meiser method. However, the complexity of intermediates in co‐reduction hampers simultaneous improvement in urea yield and Faradaic efficiency (FE). Herein, we developed a Cu/Cu2O Mott‐Schottky catalyst with nanoscale rectifying heterointerfaces through precise controllable in‐situ electroreduction of Cu2O nanowires, achieving notable FE (32.6‐47.0%) and substantial yields (6.08‐30.4 μmol h‐1 cm‐2) across a broad range of ultralow applied potentials (0 to ‐0.3 V vs. RHE). Operando synchrotron radiation‐Fourier transform infrared spectroscopy (SR‐FTIR) confirmed the formation of *CO intermediates and C‐N bonds, subsequently density functional theory (DFT) calculations deciphered that the Cu/Cu2O rectifying heterointerface modulated *CO adsorption, significantly enhancing subsequent C‐N coupling dynamics between *CO and *NOH intermediates. This work not only provides a groundbreaking and advanced pathway for C‐N coupling, but also offers deep insights into copper‐based heterointerface catalysts for urea synthesis.