A Co-based MOF supported on Ti3C2 MXene was prepared via in situ growth, which can efficiently reduce nitrogen to ammonia under environmental conditions.

As a raw material for producing chemical fertilizers, ammonia plays an essential role in human production and life. Due to the severe energy consumption and pollution caused by the industrial Haber–Bosch process of NH3 synthesis, developing the NH3 synthesis reaction under ambient conditions is vital. Electrochemical nitrogen reduction reaction (NRR) has recently emerged as a potential method. However, its limited NH3 yield and selectivity are unsatisfactory. NO3 −, as an oxidized form of nitrogen, universally exists in drinking water (<50 mg L−1) and industrial wastewater (2000‐4000 mg L−1). Electrochemical nitrate reduction reaction (NO3 −RR), with higher production and Faradaic efficiency, is a promising strategy for water treatment and NH3 production. In this review, a detailed overview of the recent progress in NO3 −RR for NH3 production with precious group metal (PGM) electrocatalysts, PGM‐free electrocatalysts, and nonmetal electrocatalysts is summarized. In addition, effective design strategies for efficient electrocatalysts, existing challenges, and research prospects for the next stage are also discussed. This review may provide some directions for improving efficient electrocatalysts in electrocatalytic NO3 −RR and offer inspiration for the electrochemical ammonia synthesis process.

As one of the most important chemicals and carbon‐free energy carriers, ammonia (NH3) has significant energy‐related applications in industry and agriculture. Ninety percent of NH3 is produced by the Haber–Bosch process using high‐purity N2 and H2 at high temperatures and pressures, which consumes about 1% of the total energy production and causes 1.4% of global CO2 emissions. The environmentally friendly electrochemical nitrogen reduction reaction (NRR) with low energy consumption is a promising alternative to the conventional Haber–Bosch process. However, the main issue is the low Faradaic efficiency and NH3 selectivity of electrochemical NRR, caused by inert nitrogen molecules and competitive hydrogen evolution reaction. As one of the cheapest and most abundant transition metals widely utilized in the Haber–Bosch process, the Fe element has presented the potential high performance for the electrochemical NRR. This article summarizes recent advances and research progress in non‐noble Fe‐based catalysts used for NH3 electrosynthesis. Various synthetic protocols, structure/morphology modification, performance improvement, and reaction mechanisms are comprehensively presented. Based on recent experimental and theoretical studies, we aim to illuminate the structure–property relationship and offer an excellent opportunity for engineering advanced Fe‐based catalysts for nitrogen fixation. The most critical challenges and opportunities for Fe‐based catalysts are also provided. This review would open up a promising avenue toward developing platinum‐group‐metal‐free catalysts for electrochemical NRR applications in the future.