A Theoretical Perspective for Ammonia Synthesis: Nitric Oxide or Nitrate Electroreduction?

Abstract Ammonia is an important raw material for agricultural production, playing a key role in global food production. However, conventional ammonia synthesis resulted in extensive greenhouse gas emissions and huge energy consumption. Recently, researchers have proposed electrocatalytic reverse artificial nitrogen cycle (eRANC) routes to circumvent these issues, which can be driven by electrocatalysis and sustainable electricity. Here, a theoretical and computational perspective on the challenges and opportunities with the comparison with experimental results: electrochemical reduction of nitrate (eNO 3 RR) and nitrite (eNO 2 RR), electrochemical reduction of nitric oxide (eNORR) combined with oxidative nitrogen fixation are presented. By comparison, the N 2 →NO→NH 3 route is proposed as the most promising in case the NO solubility can be solved well in reactor design. Its high efficiency of ammonia production is demonstrated. Instead, the eNO 3 RR can be another choice because it is non‐toxic and the solid‐liquid interface is usually efficient for electrochemical reactions, while its low selectivity at low overpotentials is an issue. These fundamentals highlight the potential and key factors of eRANC as an efficient and sustainable route for ammonia production.