Ag‐Co3O4‐CoOOH‐Nanowires Tandem Catalyst for Efficient Electrocatalytic Conversion of Nitrate to Ammonia at Low Overpotential via Triple Reactions

The electrocatalytic conversion of nitrate (NO3‾) to NH3 (NO3RR) offers a promising alternative to the Haber–Bosch process. However, the overall kinetic rate of NO3RR is plagued by the complex proton‐assisted multiple‐electron transfer process. Herein, Ag/Co3O4/CoOOH nanowires (i‐Ag/Co3O4 NWs) tandem catalyst is designed to optimize the kinetic rate of intermediate reaction for NO3RR simultaneously. The authors proved that NO3‾ ions are reduced to NO2‾ preferentially on Ag phases and then NO2‾ to NO on Co3O4 phases. The CoOOH phases catalyze NO reduction to NH3 via NH2OH intermediate. This unique catalyst efficiently converts NO3‾ to NH3 through a triple reaction with a high Faradaic efficiency (FE) of 94.3% and a high NH3 yield rate of 253.7 μmol h−1 cm−2 in 1 M KOH and 0.1 M KNO3 solution at ‒0.25 V versus RHE. The kinetic studies demonstrate that converting NH2OH into NH3 is the rate‐determining step (RDS) with an energy barrier of 0.151 eV over i‐Ag/Co3O4 NWs. Further applying i‐Ag/Co3O4 NWs as the cathode material, a novel Zn‐nitrate battery exhibits a power density of 2.56 mW cm−2 and an FE of 91.4% for NH3 production. The Ag/Co3O4/CoOOH nanowires (i‐Ag/Co3O4 NWs) tandem catalyst is designed to optimize the kinetic rate of intermediate reaction for NO3RR simultaneously. The kinetic studies reveal that NO3‾ ions are reduced to NO2‾ preferentially on Ag phases, and then the NO2‾ intermediates are converted to NO on Co3O4 phases. The CoOOH phases catalyze NO reduction to NH3 via the NH2OH intermediate.