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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Mg3N2 by Materials Project

Mg3N2 is Corundum-like structured and crystallizes in the cubic Ia-3 space group. The structure is three-dimensional. Mg2+ is bonded to four N3- atoms to form a mixture of corner and edge-sharing MgN4 tetrahedra. There are a spread of Mg–N bond distances ranging from 2.10–2.20 Å. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded to six equivalent Mg2+ atoms to form a mixture of corner and edge-sharing NMg6 octahedra. The corner-sharing octahedral tilt angles are 55°. In the second N3- site, N3- is bonded to six equivalent Mg2+ atoms to form a mixture of distorted corner and edge-sharing NMg6 octahedra. The corner-sharing octahedra tilt angles range from 55–56°.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Magnesium‐Mediated Electrochemical Synthesis of Ammonia

Metal-mediated electrochemical synthesis of ammonia (NH3) is a promising method to activate N2 at room temperature. While a Li-mediated approach has been optimized to produce NH3 at high current density and selectivity, Li's scarcity and its highly negative plating potential limit scalability and energy efficiency. Alternative mediators have been proposed, but only Ca has shown some promise, achieving ≈50% Faradaic efficiency (FE), though requiring voltages beyond -3 V. Here, we report a Mg-mediated nitrogen reduction reaction (Mg-NRR), where N2 is activated on Mg to form Mg3N2, followed by protolysis to release NH3 and regenerate Mg. A notable NH3 FE of 25.28 ± 3.80% is achieved at a current density of -45 mA cm-2, corresponding to an NH3 partial current density of -11.30 ± 1.77 mA cm-2 under 6 bar N2. Isotope-labeled experiments confirm that NH3 originates from N2, with similar FE (25.15 ± 1.01%). Importantly, NH3 production is demonstrated at a total cell potential as low as -3 V. This Li-free Mg-NRR system offers key advantages, including lower energy input and use of earth-abundant materials, making it a scalable route for sustainable NH3 synthesis.

Goyal, Ishita↗