Dissociative N₂ Activation on Dual-Atom Catalysts Driven by Symmetric d-Electron Configuration for Urea...

Electrochemical urea synthesis offers a sustainable alternative to the energy-intensive Bosch-Meiser process but is hindered by N₂ inertness and inefficient C-N bond formation. Herein, we propose a dissociative mechanism in which molecular N₂ is initially activated and fragmented into surface-bound nitrogen intermediates for subsequent C-N coupling. Nitrogen-doped graphene-supported dual-atom (MN₄-MN₄) catalysts with ∼4 Å intersite distance enable side-on N₂ adsorption across adjacent metal centers, facilitating cooperative bond dissociation. Density functional theory (DFT) calculations combined with machine learning (ML) analysis on 28 homonuclear MN₄-MN₄ catalysts identify MoN₄-MoN₄ and TcN₄-TcN₄ as highly active candidates, exhibiting low limiting potentials and favorable kinetics for urea formation. Sure independence screening and sparsifying operator (SISSO)-derived descriptors further establish an interpretable connection between N₂ dissociation and the atomic-level electronic properties of the active metal sites, emphasizing the pivotal role of symmetric d-electron configuration. These findings uncover fundamental structure-activity relationships and furnish a rational design strategy for efficient and sustainable urea electrocatalysts.