Hydrated molten salt electrolytes effectively promote electrocatalytic NH3 synthesis at low temperatures

In the field of electrocatalytic nitrogen reduction reaction (NRR), molten salt is used as a unique electrolyte due to its advantages of high N 2 solubility and wide electrochemical window. However, it has failed to be widely used due to its high reaction temperature (mostly > 200 °C) and low yield. Herein, a novel low-temperature (<100 °C) electrolysis system with hydrated molten salt hybrid electrolyte is designed. This system exhibits an ammonia yield of 1.003 × 10 −8 mol s −1 cm −2 (−0.7 V vs. SCE) at 60 °C. Faradaic efficiency (FE) reaches 80.45 % (−0.65 V vs. SCE). The NH 3 yield and FE are increased by 18.6 and 2 times compared to the previously reported low-temperature system, respectively. Linear sweep voltammetry (LSV), in situ Raman and in situ Fourier Transform-Infrared (FT-IR) experiments show that solid crystalline water can be used as a hydrogen source to effectively promote NRR while inhibiting the hydrogen evolution reaction (HER). Molecular dynamics (MD) experiments confirm that the electrolyte system maintains a high N 2 solubility and mass transfer rate.