Phase‐Controlled Copper Catalysts Derived from ZIFs for Electrochemical Urea Synthesis via CO ₂ and Nitrate Reduction

ABSTRACT Electrochemical urea synthesis from CO ₂ and nitrate is a promising route for sustainable fertilizer production, yet the role of different catalyst phases remains unclear. Here, we report a phase‐controlled copper catalyst system derived from Cu‐doped ZIF‐8, enabling a transition from atomically dispersed Cu─N sites to metallic Cu nanoparticles within N‐doped carbon frameworks. Among them, the Cu─N coordinated catalyst exhibits superior performance, delivering the lowest onset potential and highest selectivity in H‐cell measurements. In a flow cell, it optimized a faradaic efficiency of 49% and a urea yield rate of 2,970 mg g ⁻¹ h ⁻¹ at −0.5 V vs RHE. Mechanistic studies reveal that Cu single‐atom sites facilitate C─N coupling and lower the energy barrier for urea desorption. Electronic structure analysis indicates optimized intermediate binding, suppressing competing reactions. These findings highlight the importance of phase‐controlled Cu catalysts for efficient urea electrosynthesis.