Cost-effective
and nonprecious iron-based catalysts were synthesized,
evaluated, and compared for electrocatalytic N2 reduction
reaction (NRR) under alkaline conditions in the potential range from
−0.4 to 0.1 V [vs reversible hydrogen electrode (RHE)] at low
temperature (≤60 °C) and atmospheric pressure. The tested
H-type cell was separated by an anion exchange membrane in 6 M KOH
alkaline electrolyte (pH = over 14) in order to minimize hydrogen
evolution reaction and to directly form NH3 gas. The amount
of ammonia synthesized was quantified using an indophenol blue method
and cross-checked with 1H nuclear magnetic resonance spectroscopy
and ion chromatography using both 14N2 and 15N2 gases. Because of the synergistic effect between
the Fe3C, Fe2O3, and Fe composites
in the NRR, both the ammonia formation rate and faradaic efficiency
in Fe3C/Fe2O3/Fe/C were approximately
fourfold higher than those in Fe2O3/C at 60
°C and 0.1 V (vs RHE). These results can provide insights into
designing Fe-based electrocatalysts for NRR at atmospheric pressure.