United in Nitride: The Highly Condensed Boron Phosphorus Nitride BP₃N₆

Abstract

Owing to intriguing materials properties non‐metal nitrides are of special interest for both, solid‐state chemistry and materials science. Mixed ternary non‐metal nitrides, however, have only been sparsely investigated, as preparative chemistry lacks a systematic access, yet. Herein, we report on the highly condensed boron phosphorus nitride BP3N6, which was synthesized from (PNCl2)3, NH4N3 and h‐BN in a high‐pressure high‐temperature reaction. By increasing partial pressure of HCl during synthesis using NH4Cl, single‐crystals of BP3N6 up to 80 μm in length were obtained. The unprecedented framework‐type structure determined by single‐crystal XRD blends structural motifs of both, α‐P3N5 and c‐BN, rendering BP3N6 a double nitride. The compound was further investigated by Rietveld refinement, EDX, temperature‐dependent PXRD, FTIR and solid‐state NMR spectroscopy. The formation of BP3N6 through use of reactive precursors exemplifies an innovative access to mixed non‐metal nitrides.

Nitride Synthesis under High-Pressure, High-Temperature Conditions: Unprecedented In Situ Insight into the Reaction

“…Over the past 30 years, several synthetic methods for phosphorus nitrides and nitridophosphates under high-pressure, high-temperature conditions have emerged, including some mechanistic suggestions: the solid-state metathesis, the Li 3 N self-flux method, the nitride route, and the azide route as well as NH 4 Cl-, HCl-, and NH 4 F-assisted syntheses. − Starting from LiPN 2 and a metal halide, the solid-state metathesis uses the formation of the corresponding lithium halide as the reaction driving force . Additionally, lithium halide, which is molten at reaction conditions, acts as a flux agent supporting single-crystal growth.…”

“…Transferring the well-known ion exchange to high-pressure, high-temperature syntheses, it was shown that a preservation of a P/N framework is possible . Recently, in situ -generated HCl and HF were used to activate inert starting materials such as BN or even TiN. , It is assumed that reactive intermediate species are formed during the reaction process. The azide route uses P 3 N 5 and a metal azide as the reactant, which is suggested to decompose under elevated pressure, releasing molecular N 2 , the partial pressure of which further inhibits the decomposition of nitrides .…”

Synthesis of Nitride Zeolites in a Hot Isostatic Press

“…However, sample quantities have intrinsically been limited by high-pressure techniques. [5][6][7][8][9] Investigations on the associated optical and physical properties of nitridophosphates, such as ion conductivity or luminescence, have however quickly revealed the potential of this functional materials class. [5,[10][11][12] In particular, the intriguing luminescence properties of nitridophosphates like Ba3P5N10X:Eu 2+ (X = Cl, Br, I) and AEP8N14:Eu 2+ (AE = Ca, Sr, Ba) clearly underline the quest for a synthetic approach that can be transformed to a large batch scale.…”