Ambient Electrocatalytic Urea Synthesis From CO₂ and N₂ Compartmentalized by Cyclic Cu-Trinuclear (Cu₃)-Ferrocene...

Direct electrocatalytic co-reduction of N₂ and CO₂ 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, Cu₃Fc-Pyz-POP, derived from in situ formed Cu₃(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 N₂ and CO₂, thereby promoting selective urea formation under ambient conditions. Operated in a 0.1 M KHCO₃ electrolyte under ambient conditions, Cu₃Fc-Pyz-POP delivers an exceptional urea yield rate of 115.23 µgh^-1mg^-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 N₂ and CO₂ intermediates. Our finding establishes M-POPs as promising platforms for ambient urea electrosynthesis, contributing to energy-efficient fertilizer production and advancing low-carbon chemistry.