Boosting Urea Electrosynthesis via Asymmetric Oxygen Vacancies in Zn‐doped Fe2O3 Catalysts

Urea electrosynthesis from CO2 and nitrate (NO3‐) provides an attractive pathway for storing renewable electricity and substitute traditional energy‐intensive urea synthesis technology. However, the kinetics mismatching between CO2 reduction and NO3‐ reduction, as well as the difficulty of C‐N coupling, are major challenges in urea electrosynthesis. Herein, we first calculated the free energy of *CO, *OCNO and *NOH formation over defect‐rich Fe2O3 catalysts with different metal dopants, which showed that Zn dopant was a promising candidate. Based on the theoretical study, we developed Zn‐doped defect‐rich Fe2O3 catalysts (Zn‐Fe2O3/OV) containing asymmetric Zn‐OV‐Fe sites. It exhibited an outstanding urea Faradaic efficiency of 62.4% and the remarkable recycling stability. The production rate of urea was as high as 7.48 mg h‐1 mgcat‐1, which is higher than most of the reported works up to date. Detailed control experiments and in situ spectroscopy analyses identified *OCNO as a crucial intermediate for C‐N coupling. The Zn‐Fe2O3/OV catalyst with asymmetric Zn‐OV‐Fe sites showed enhanced *CO coverage and promoted *OCNO formation, leading to high efficiency toward urea production.