Pd─O─Cu Bridging Promotes Co‐Adsorption of CO and NH ₂ Intermediates for Efficient Electrocatalytic Urea Synthesis Over Pd‐La _1.6 CuO ₄

ABSTRACT Electrocatalytic urea synthesis from CO 2 and nitrate (NO 3 − ) represents a promising route for carbon mitigation and sustainable chemical production. However, the efficiency of this process remains limited, largely due to the high energy barrier of C─N coupling step, resulting in low Faradaic efficiency (FE) and yield rate. Herein, Pd nanoclusters anchored on La 1.6 CuO 4 nanofibers (Pd‐La 1.6 CuO 4 ) were constructed to promote the interfacial interaction via Pd─O─Cu bridging for electrocatalytic urea synthesis. Such a configuration facilitates the electron transfer from Cu to Pd and promotes the co‐adsorption of C/N‐containing intermediates ( * CO and * NH 2 ), thereby boosting the urea synthesis with a high FE of 56.25% and promising yield rate of 241.75 µg·h −1 ·mg cat −1 . Operando electrochemical spectroscopy confirms the formation of key intermediates ( * NH 2 and * CONH 2 ), suggesting that * CO couples with * NH 2 to form * CONH 2 , which then converts to CO(NH 2 ) 2 at the Pd─O─Cu sites. Theoretical calculations reveal that Pd 4d ‐O 2p ‐Cu 3d orbital hybridization creates a continuous electronic structure near the Fermi level, which lowers the C─N coupling energy barrier for the rate‐determining step from * CONH 2 to CO(NH 2 ) 2 . This work presents a strategy based on the co‐adsorption of C/N‐containing intermediates for highly efficient urea synthesis and advances the research on Cu‐based perovskite oxide electrocatalysts.