Crystalline Nitridophosphates by Ammonothermal Synthesis
Mathias Mallmann, Sebastian Wendl, Wolfgang Schnick
Abstract
Abstract Nitridophosphates are a well‐studied class of compounds with high structural diversity. However, their synthesis is quite challenging, particularly due to the limited thermal stability of starting materials like P 3 N 5 . Typically, it requires even high‐pressure techniques (e.g. multianvil) in most cases. Herein, we establish the ammonothermal method as a versatile synthetic tool to access nitridophosphates with different degrees of condensation. α‐Li 10 P 4 N 10 , β‐Li 10 P 4 N 10 , Li 18 P 6 N 16 , Ca 2 PN 3 , SrP 8 N 14 , and LiPN 2 were synthesized in supercritical NH 3 at temperatures and pressures up to 1070 K and 200 MPa employing ammonobasic conditions. The products were analyzed by powder X‐ray diffraction, energy dispersive X‐ray spectroscopy, and FTIR spectroscopy. Moreover, we established red phosphorus as a starting material for nitridophosphate synthesis instead of commonly used and not readily available precursors, such as P 3 N 5 . This opens a promising preparative access to the emerging compound class of nitridophosphates.