Liquid ammonia is considered a sustainable liquid fuel and an easily transportable carrier of hydrogen energy; however, its synthesis processes are energy-consuming, high cost, and low yield rate. Herein, we report the electrocatalytic reduction of nitrate (NO3 –) (ERN) to ammonia (NH3) with nickel phosphide (Ni2P) used as a noble metal-free cathode. Ni2P with (111) facet was grown in situ on nickel foam (NFP), which was regarded as a self-supporting cathode for ERN to synthesis NH3 with high yield rate (0.056 mmol h–1 mg–1) and superior faradaic efficiency of 99.23%. The derived atomic H (*H), verified by a quenching experiment and an electron spin resonance (ESR) technique, effectively enhanced the high selectivity for NH3 generation. DFT calculations indicated that *NO3 was deoxygenated to *NO2 and *NO, and *NO was subsequently hydrogenated with *H to generate NH3 with an energy releasing process (ΔG < 0). OLEMS also proved that NO was the merely gas intermediate. NFP exhibited the unique superhydrophilic surface, metallic properties, low impedance, and abundant surface sites, favorable for adsorption of NO3 –, generation of *H, and then hydrogenation of NO3 –. Hence, NFP cathode showed high selectivity for NH3 (89.1%) in ERN. NFP with long-term stability and low energy consumption provides a facile strategy for synthesis of NH3 and elimination of NO3 – contamination.

In the catalytic transformation of biomass into valuable chemicals, it is extremely important to inhibit undesirable reactions to increase the yield of target products.