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(010)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.
