Redox‐Mediated Ambient Electrolytic Nitrogen Reduction for Hydrazine and Ammonia Generation

Abstract This work presents a redox‐mediated electrolytic nitrogen reduction reaction (RM‐eNRR) using polyoxometalate (POM) as the electron and proton carrier which frees the TiO 2 ‐based catalyst from the electrode and shifts the reduction of nitrogen to a reactor tank. The RM‐eNRR process has achieved an ammonium production yield of 25.1 μg h −1 or 5.0 μg h −1 cm −2 at an ammonium concentration of 6.7 ppm. With high catalyst loading, 61.0 ppm ammonium was accumulated in the electrolyte upon continuous operation, which is the highest concentration detected for ambient eNRR so far. The mechanism underlying the RM‐eNRR was scrutinized both experimentally and computationally to delineate the POM‐mediated charge transfer and hydrogenation process of nitrogen molecule on the catalyst. RM‐eNRR is expected to provide an implementable solution to overcome the limitations in the conventional eNRR process.