Urea synthesis via thermal catalytic coupling of N2 with CO2 on singly dispersed Co1Ru3 bimetallic clusters: a theoretical perspective

• • Co1Ru3@Mo2CO2 exhibits a low rate-determining energy barrier of 1.16 eV for *NHNH2 → *NH2NH2 conversion, enabling thermal urea synthesis under mild conditions (780 K, 29 bar) with a turnover frequency of 1.01 × 10−3 s−1 site−1, which is industrially relevant for reducing energy input compared to conventional processes. • • The catalyst demonstrates excellent thermodynamic stability and synergistic activation of N2, CO2, and H2, fulfilling prerequisites for direct coupling; this stability is critical for long-term operation under industrial conditions. • • The associative pathway facilitates direct N–C coupling, bypassing the energy-intensive Haber–Bosch NH3 synthesis step, potentially reducing overall energy demand and CO2 emissions in urea production. • • The Co1Ru3 bimetallic cluster precisely modulates charge transfer between support and intermediates, enhancing electrophilicity of *CO and promoting nucleophilic attack by *NH2, which is essential for efficient C–N bond formation and high selectivity.