Dissociative N 2 Activation on Dual-Atom Catalysts Driven by Symmetric d -Electron Configuration for Urea Electrosynthesis

Electrochemical urea synthesis offers a sustainable alternative to the energy-intensive Bosch-Meiser process but is hindered by N 2 inertness and inefficient C–N bond formation. Herein, we propose a dissociative mechanism in which molecular N 2 is initially activated and fragmented into surface-bound nitrogen intermediates for subsequent C–N coupling. Nitrogen-doped graphene-supported dual-atom (MN 4 –MN 4 ) catalysts with ∼4 Å intersite distance enable side-on N 2 adsorption across adjacent metal centers, facilitating cooperative bond dissociation. Density functional theory (DFT) calculations combined with machine learning (ML) analysis on 28 homonuclear MN 4 –MN 4 catalysts identify MoN 4 –MoN 4 and TcN 4 –TcN 4 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 N 2 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.