Cerium-promoted conversion of dinitrogen into high-energy-density material CeN6 under moderate pressure

Synthesis pressure and structural stability are two crucial factors for highly energetic materials, and recent investigations have indicated that cerium is an efficient catalyst for N2 reduction reactions. Here, we systematically explore Ce–N compounds through first-principles calculations, demonstrating that the cerium atom can weaken the strength of the N≡N bond and that a rich variety of cerium polynitrides can be formed under moderate pressure. Significantly, P1̄-CeN6 possesses the lowest synthesis pressure of 32 GPa among layered metal polynitrides owing to the strong ligand effect of cerium. The layered structure of P1̄-CeN6 proposed here consists of novel N14 ring. To clarify the formation mechanism of P1̄-CeN6, the reaction path Ce + 3N2 → trans-CeN6 → P1̄-CeN6 is proposed. In addition, P1̄-CeN6 possesses high hardness (20.73 GPa) and can be quenched to ambient conditions. Charge transfer between cerium atoms and N14 rings plays a crucial role in structural stability. Furthermore, the volumetric energy density (11.20 kJ/cm3) of P1̄-CeN6 is much larger than that of TNT (7.05 kJ/cm3), and its detonation pressure (128.95 GPa) and detonation velocity (13.60 km/s) are respectively about seven times and twice those of TNT, and it is therefore a promising high-energy-density material.