Ferroelectric Heterojunction with Spatiotemporally Programmable CO Spillover Pathways Boosts Urea Electrosynthesis

Electrochemical urea synthesis offers a sustainable strategy for the purification and resource utilization of greenhouse gases and water pollutants. However, kinetic disparities between the competing reduction pathways of CO 2 and NO 3 – lead to spatiotemporal mismatches between C- and N-intermediates, severely hindering efficient C–N coupling. In this context, we demonstrated a strategic design of enzyme-inspired “spatial decoupling–temporal coupling” on a ferroelectric SnS-Cu 0.15 -TiO 2 heterojunction. A high urea yield rate of 2392.5 μg h –1 mg cat –1 with a Faradaic efficiency (FE) of 71.2% outperforms the state-of-the-art electrocatalysts. Atomically dispersed Cu 1 sites induce an unprecedented ferroelectricity enhancement, whereby a strengthened built-in electric field generates spatially resolved charge domains for coactivation of both CO 2 and NO 3 – . Correlated in situ Raman and infrared spectroscopic studies disclose that the S-Cu 1 -O interfacial channels mediate remote *CO spillover and its dynamic, temporal coupling with *NH 2 . Moreover, a coupled electrolyzer integrating the electrocatalytic upcycling of wastewater-derived NO 3 – and Cl – achieves a remarkable 79.4% urea FE, while enabling simultaneous environmental remediation. This work highlights the unique advantages of ferroelectric heterojunctions-mediated dynamic catalysis in regulating complex reaction networks for urea electrosynthesis, opening sustainable electrochemical routes toward CO 2 mitigation and the green transformation of coastal wastewater treatment.