Dual-metal synergy in electrocatalytic urea synthesis: mechanistic study of Fe-doped W₁₈O₄₉(010) for CO₂ and NO₃⁻ coupling

Abstract

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.

Keywords

urea electrosynthesis / dual-metal synergy / heteronuclear doping / C─N coupling

Acknowledgements

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (22403014, 21673036), the Youth Development Foundation of Jilin Prov. (20230508183RC), and the Fundamental Research Funds for the Central Universities (2412022ZD050, 2412023QD012).

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