Ambient Electrocatalytic Urea Synthesis From CO ₂ and N ₂ Compartmentalized by Cyclic Cu‐Trinuclear (Cu ₃ )‐Ferrocene (Fc) Networking Porous‐Organic‐Polymer

ABSTRACT Direct electrocatalytic co‐reduction of N ₂ and CO ₂ to urea remains constrained by sluggish kinetics and the absence of frameworks capable of concurrently activating both molecules. Herein, we present the first realization of a metalated porous organic polymer ( M‐POP )‐based electrocatalyst, Cu ₃ Fc‐Pyz‐POP , derived from in situ formed Cu ₃ (pyrazolate) triangular motif and 1,1′‐ferrocenedicarboxaldehyde through a template‐free Schiff base polymerization. The heterometallic Cu–Fe framework hosts atomically dispersed single‐site active centers that cooperatively activate and co‐reduce molecular N ₂ and CO ₂ , thereby promoting selective urea formation under ambient conditions. Operated in a 0.1 M KHCO ₃ electrolyte under ambient conditions, Cu ₃ Fc‐Pyz‐POP delivers an exceptional urea yield rate of 115.23 µgh ⁻¹ mg ⁻¹ and a Faradaic efficiency of 20.68% at –0.6 V vs RHE, surpassing its monometallic analogues. The catalyst exhibits excellent recyclability over 10 cycles and maintains stable performance during 45 h of continuous electrolysis. in situ FT‐IR spectroscopic investigation and DFT computational studies reveal that ferrocene (Fc) moieties facilitate enhanced conductivity with a dramatic decrease of HOMO‐LUMO energy gap and selective C‐N coupling between N ₂ and CO ₂ intermediates. Our finding establishes M‐POPs as promising platforms for ambient urea electrosynthesis, contributing to energy‐efficient fertilizer production and advancing low‐carbon chemistry.