A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface

Abstract Electrocatalytic C−N coupling process is indeed a sustainable alternative for direct urea synthesis and co‐upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C−N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C−N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li + <Na + <Cs + <K + . In the presence of K + , a world‐record performance was achieved with a urea yield rate of 212.8±10.6 mmol h −1 g −1 on a single‐atom Co supported TiO 2 catalyst at −0.80 V versus reversible hydrogen electrode. Theoretical calculations and operando synchrotron‐radiation Fourier transform infrared measurements revealed that the energy barriers of C−N coupling were significantly decreased via K + mediated intermediate assembly. By applying this strategy to various catalysts, we demonstrate that intermediate assembly at the electrode/electrolyte interface is a universal approach to boost sustainable urea synthesis.