Dynamic Control of Asymmetric Charge Distribution for Electrocatalytic Urea Synthesis

Abstract Constructing dual catalytic sites with charge density differences is an efficient way to promote urea electrosynthesis from parallel and CO₂ reduction yet still challenging in static system. Herein, a dynamic system is constructed by precisely controlling the asymmetric charge density distribution in an Au‐doped coplanar Cu₇ clusters‐based 3D framework catalyst (Au@cpCu₇CF). In Au@cpCu₇CF, the redistributed charge between Au and Cu atoms changed periodically with the application of pulse potentials switching between −0.2 and −0.6 V and greatly facilitated the electrosynthesis of urea. Compared with the static condition of pristine cpCu₇CF (FE_urea = 5.10%), the FE_urea of Au@cpCu₇CF under pulsed potentials is up to 55.53%. Theoretical calculations demonstrated that the high potential of −0.6 V improved the adsorption of ^*HNO₂ and ^*NH₂ on Au atoms and inhibited the reaction pathways of by‐products. While at the low potential of −0.2 V, the charge distribution between Au and Cu atomic sites facilitated the thermodynamic C–N coupling step. This work demonstrated the important role of asymmetric charge distribution under dynamic regulation for urea electrosynthesis, providing a new inspiration for precise control of electrocatalysis.