Tip‐Induced Self‐Enhanced Concentration Gradients Catalyst for Sustainable Electrocatalytic Urea Synthesis

ABSTRACT Electrocatalytic C─N coupling via the co‐reduction of CO ₂ and NO ₃ ⁻ represents a promising route for sustainable urea synthesis under ambient conditions, simultaneously addressing critical challenges in energy sustainability and environmental remediation. However, its practical implementation is hindered by sluggish C─N coupling kinetics and the competing hydrogen evolution reaction (HER), which severely restricts energy conversion efficiency. Herein, we propose a tip‐induced local electric field strategy that generates a self‐enhanced concentration gradient to promote electrocatalytic C─N coupling. By constructing densely aligned Co ₃ O ₄ nanoneedles on carbon cloth, an outstanding electrocatalytic performance was achieved, requiring only an ultra‐low potential of −0.60 V versus reversible hydrogen electrode (RHE) while delivering a high urea yield rate of 49.63 umol h ⁻¹ cm ⁻² and a Faradic efficiency of 21.37%. Finite element simulations reveal that the nanoscale high‐curvature tip generates an intensified local electric field, enriching potassium ions (K ⁺ ) at the electrode‐electrolyte interface to stabilize key intermediates and direct the reaction pathway toward C─N coupling. Moreover, a series of operando spectroscopic characterizations provide direct evidence for enhanced C─N coupling process under an intensified local electric field. This work offers a generalizable strategy for energy‐efficient C─N coupling, paving the way for sustainable utilization of nitrogen and carbon resources.