Screening of transition metal and boron atoms co-doped graphdiyne catalysts for electrocatalytic urea synthesis

Electrocatalytic C-N coupling using nitrogen (N2) and carbon dioxide (CO2) as precursors offers a promising alternative for urea production under mild conditions, compared to traditional synthesis approaches. However, the design and screening of extremely efficient electrocatalysts remains a significant challenge in this field. Hence, we propose a systematic approach to screen efficient double-atom catalysts (DACs) with both metal and boron active sites, employing density functional theory (DFT). A comprehensive evaluation of 27 potential catalysts were performed, taking into account their stability, co-adsorption of N2 and CO2, as well as the potential-determining step (PDS) involved urea formation. The calculated results show that co-doped graphdiyne with CrB and MnB double atoms (CrB@GDY and MnB@GDY) emerge as potential electrocatalysts for urea production, displaying thermodynamic energy barriers of 0.41 eV and 0.66 eV, respectively. More importantly, these two DACs can significantly suppress the ammonia (NH3) and C1 products formation. Furthermore, a catalytic activity relationship between the d-band centers of the DACs and urea production performance were established. This study not only forecasts two promising DACs for subsequent experimental work but also establishes a theoretical framework for the evaluation of DACs in electrocatalytic urea synthesis.