The electrochemical nitrate reduction reaction (NO3RR)
is an attractive green alternative to the conventional Haber–Bosch
method for the synthesis of NH3. However, this reaction
is a tandem process that involves multiple steps of electrons and
protons, posing a significant challenge to the efficient synthesis
of NH3. Herein, we report a high-rate NO3RR
electrocatalyst of Fe and Cu double-doped Co3O4 nanorod (Fe1/Cu2-Co3O4) with abundant oxygen vacancies, where the Cu preferentially catalyzes
the rapid conversion of NO3
– to NO2
– and the oxygen vacancy in the Co3O4 substrate can accelerate NO2
– reduction to NH3. In addition, the introduction of Fe
can efficiently capture atomic H* that promotes the dynamics of NO2
– to NH3, improving Faradaic
efficiency of the produced NH3. Controlled experimental
results show that the optimal electrocatalyst of Fe1/Cu2-Co3O4 exhibits good performance with
high conversion (93.39%), Faradaic efficiency (98.15%), and ammonia
selectivity (98.19%), which is significantly better than other Co-based
materials. This work provides guidance for the rational design of
high-performance NO3RR catalysts.