Efficient urea electrosynthesis via dual-atom catalysts enabled by strong p-d orbital coupling

Efficient urea electrosynthesis via dual-atom catalysts enabled by strong p-d orbital coupling

Electrocatalytic urea synthesis via C-N coupling offers a sustainable alternative to conventional methods, addressing energy and environmental challenges. However, the design of efficient catalysts involves diverse reactions and intermediates due to the multistep nature of the process. Double atom catalysts (DACs), with their enhanced co-adsorption sites, facilitate the activation of multiple species during electrocatalytic reactions. Using density functional theory (DFT) calculations, we for the first time investigate CuM@N6-G (M = B, Al, Ga, In) catalysts—d-block Cu and p-block atoms embedded in N-doped graphene—as stable DACs for urea synthesis. These catalysts possess strong d-p orbital coupling that enable effective co-adsorption and activation of NO and CO, supporting consecutive C-N coupling and proton-electron transfer steps, which predict high urea production performance. Notably, their low limiting potentials indicate excellent catalytic activity, while the hydrogen evolution reaction (HER) and protonation of *NO and *CO can be suppressed to ensure high urea selectivity. This study provides a theoretical framework for rational design of novel DACs in urea electrocatalysis to guide future experiments.