High-pressure synthesis of ultraincompressible hard rhenium nitride pernitride Re$_{2}$(N$_{2}$)N$_{2}$ stable at ambient conditions

TL;DR

This paper reports the synthesis and characterization of a novel, ultrahard, and ultraincompressible rhenium nitride pernitride Re₂(N₂)N₂, which is stable at ambient conditions and exhibits unique crystal chemistry and exceptional properties.

Contribution

It introduces a new rhenium nitride pernitride with unique crystal chemistry and demonstrates a scalable synthesis method from high-pressure to ambient conditions.

Findings

Re₂(N₂)N₂ has a bulk modulus of 428 GPa.

It exhibits a nanoindentation hardness of 36.7 GPa.

The material is recoverable at ambient conditions.

Abstract

Here we report the synthesis of metallic, ultraincompressible (bulk modulus $K_{0}$ = 428(10) GPa) and very hard (nanoindentation hardness 36.7(8) GPa) rhenium (V) nitride pernitride Re$_{2}$(N$_{2}$)N$_{2}$. While the empirical chemical formula of the compound, ReN$_{2}$, is the same as for other known transition metals pernitrides, e.g. IrN$_{2}$, PtN$_{2}$, PdN$_{2}$ and OsN$_{2}$, its crystal chemistry is unique. The known pernitrides of transition metals consist of a metal in the oxidation state +IV and pernitride anions N$_{2}^{4-}$. ReN$_{2}$ contains both pernitride N$_{2}^{4-}$ and discrete N$^{3-}$ anions, which explains its exceptional properties. Moreover, in the original experimental synthesis of Re$_{2}$(N$_{2}$)N$_{2}$ performed in a laser-heated diamond anvil cell via a direct reaction between rhenium and nitrogen at pressures from 40 to 90 GPa we observed that the material was recoverable at ambient conditions. Consequently, we developed a route to scale up its synthesis through a reaction between rhenium and ammonium azide, NH$_{4}$N$_{3}$, in a large-volume press at 33 GPa. Our work resulted not only in a discovery of a novel material with unusual crystal chemistry and a set of properties attractive for potential applications, but also demonstrated a feasibility of surmounting conceptions common in material sciences.