The electrocatalytic co-reduction of carbon dioxide (CO2) and nitrate (NO3-) to urea represents a promising dual-purpose strategy, offering a sustainable alternative to the energy-intensive Bosch-Meiser process while simultaneously mitigating environmental pollutants. This study systematically explores the catalytic performance of a series of transition-metal-doped W18O49 (0 1 0) surfaces (TM-W18O49, TM = Fe, Co, Ni, Cu, Zn) for urea synthesis using first-principles calculations. Among them, Fe-doped W18O49 emerges as the most promising electrocatalyst, exhibiting superior activity with a remarkably low limiting potential of -0.46 V (compared to -0.95 V for pristine W18O49) and outstanding selectivity by effectively suppressing competing nitrate reduction and hydrogen evolution reactions. Mechanistic analysis reveals a heteronuclear dual-metal (TM-W) synergistic adsorption mechanism, in which the doped transition metal and adjacent W site collaboratively activate NO3-, thereby facilitating the critical C-N bond formation. This work not only elucidates the reaction pathway and active-site synergy in Fe-W18O49, but also provides a theoretical foundation for the rational design of high-performance bimetallic oxide catalysts towards efficient electrocatalytic urea production.
Deng et al. (Thu,) studied this question.