The polymorph δ-P₃N₅ transformed into another, also previously unknown modification of P₃N₅ when the compression pressure was reduced: at seven gigapascals, the polymorph α′-P₃N₅ was formed. This is a new solid material that remains stable under normal ambient conditions. The crystal structure of this phosphoronitride is also unusual, being composed of PN₄ tetrahedra: A phosphorus atom is located in the center of these pyramid-shaped structural units, while the four "corners" are each occupied by a nitrogen atom. Compared with the well-known polymorph α-P₃N₅, which is already being discussed in research as a possible industrial material, α′-P₃N₅ has a significantly higher density. It is therefore considerably harder and potentially even more attractive in terms of potential engineering applications.
"The α′-P₃N₅ formed on decompression of δ-P₃N₅ exemplifies how nitrogen compounds with highly interesting properties can be discovered via a detour of high-pressure syntheses. Further investigations should now follow to explore potential applications of this new material. With our publication, we want to encourage more high-pressure and high-temperature research on non-metal nitrides – which have been largely neglected in comparison with metal nitrides. New studies in this exciting field can significantly expand our understanding of nitrogen chemistry. They will also potentially contribute to the discovery of recyclable materials for everyday products," says Bayreuth crystal physicist Prof. Dr. Dr. h.c. Natalia Dubrovinskaia from the Laboratory of Crystallography at the University of Bayreuth, who coordinated the research.
International cooperation:
Together with the Bavarian Research Institute of Experimental Geochemistry & Geophysics (BGI) and the Laboratory of Crystallography at the University of Bayreuth, numerous other research partners were involved in the new study: the LMU Munich, the University of Edinburgh, the University of Linköping, Shandong University in Jinan, China, the German Electron Synchrotron (DESY) in Hamburg, the European Synchrotron Radiation Facility in Grenoble, and the Center for Advanced Radiation Sources at the University of Chicago.
Publication:
Dominique Laniel et al.: Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P₃N₅, δ-P₃N₅ and PN₂. Chemistry – A European Journal (2022). DOI: https://dx.doi.org/10.1002/chem.202201998
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