Synthetic Route to Metal Nitrides: High-Pressure Solid-State Metathesis Reaction

We report a general synthetic route to well-crystallized metal nitrides through a high-pressure solid-state metathesis reaction (HPSSM) between boron nitride (BN) and ternary metal oxide A(x)M(y)O(z) (A = alkaline or alkaline-earth metal and M = main group or transition metal). On the basis of the synthetic metal nitrides (Fe3N, Re3N, VN, GaN, CrN, and WxN) and elemental products (graphite, rhenium, indium, and cobalt metals), the HPSSM reaction has been systematically investigated with regard to its general chemical equation, reaction scheme, and characteristics, and its thermodynamic considerations have been explored by density functional theory (DFT) calculations. Our results indicate that pressure plays an important role in the synthesis, which involves an ion-exchange process between boron and the metal ion, opening a new pathway for material synthesis.