Balanced NO_x⁻ and Proton Adsorption for Efficient Electrocatalytic NO_x⁻ to NH₃ Conversion

Electrocatalytic nitrate (NO₃⁻)/nitrite (NO₂⁻) reduction reaction (eNO_x⁻RR) to ammonia under ambient conditions presents a green and promising alternative to the Haber−Bosch process. Practically available NO_x⁻ sources, such as wastewater or plasma-enabled nitrogen oxidation reaction (p-NOR), typically have low NO_x⁻ concentrations. Hence, electrocatalyst engineering is important for practical eNO_x⁻RR to obtain both high NH₃ Faradaic efficiency (FE) and high yield rate. Herein, we designed balanced NO_x⁻ and proton adsorption by properly introducing Cu sites into the Fe/Fe₂O₃ electrocatalyst. During the eNO_x⁻RR process, the H adsorption is balanced, and the good NO_x⁻ affinity is maintained. As a consequence, the designed Cu-Fe/Fe₂O₃ catalyst exhibits promising performance, with an average NH₃ FE of ∼98% and an average NH₃ yield rate of 15.66 mg h^-1 cm^-2 under the low NO₃⁻ concentration (32.3 mM) of typical industrial wastewater at an applied potential of −0.6 V versus reversible hydrogen electrode (RHE). With low-power direct current p-NOR generated NO_x⁻ (23.5 mM) in KOH electrolyte, the Cu−Fe/Fe₂O₃ catalyst achieves an FE of ∼99% and a yield rate of 15.1 mg h^-1 cm^-2 for NH₃ production at −0.5 V (vs RHE). The performance achieved in this study exceeds industrialization targets for NH₃ production by exploiting two available low-concentration NO_x⁻ sources. © 2023 American Chemical Society.