High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-P3N5
Journal article, 2022
The direct chemical reactivity between phosphorus and nitrogen was induced under high-pressure and high-temperature conditions (9.1 GPa and 2000-2500 K), generated by a laser-heated diamond anvil cell and studied by synchrotron X-ray diffraction, Raman spectroscopy, and DFT calculations. alpha-P3N5 and gamma-P3N5 were identified as reaction products. The structural parameters and vibrational frequencies of gamma-P3N5 were characterized as a function of pressure during room-temperature compression and decompression to ambient conditions, determining the equation of state of the material up to 32.6 GPa and providing insight about the lattice dynamics of the unit cell during compression, which essentially proceeds through the rotation of the PN5 square pyramids and the distortion of the PN4 tetrahedra. Although the identification of alpha-P3N5 demonstrates for the first time the direct synthesis of this compound from the elements, its detection in the outer regions of the laser-heated area suggests alpha-P3N5 as an intermediate step in the progressive nitridation of phosphorus toward the formation of gamma-P3N5 with increasing coordination number of P by N from 4 to 5. No evidence of a higher-pressure phase transition was observed, excluding the existence of predicted structures containing octahedrally hexacoordinated P atoms in the investigated pressure range.
Author
Matteo Ceppatelli
LENS - European Laboratory for Non-Linear Spectroscopy
National Research Council of Italy (CNR)
Demetrio Scelta
National Research Council of Italy (CNR)
LENS - European Laboratory for Non-Linear Spectroscopy
Manuel Serrano-Ruiz
National Research Council of Italy (CNR)
Kamil Dziubek
LENS - European Laboratory for Non-Linear Spectroscopy
Fernando Izquierdo Ruiz
University of Oviedo
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
J. Manuel Recio
University of Oviedo
Gaston Garbarino
European Synchrotron Radiation Facility (ESRF)
Volodymyr Svitlyk
European Synchrotron Radiation Facility (ESRF)
Mohamed Mezouar
European Synchrotron Radiation Facility (ESRF)
Maurizio Peruzzini
National Research Council of Italy (CNR)
Roberto Bini
National Research Council of Italy (CNR)
University of Florence
LENS - European Laboratory for Non-Linear Spectroscopy
Inorganic Chemistry
0020-1669 (ISSN) 1520-510X (eISSN)
Vol. 61 31 12165-12180Subject Categories
Inorganic Chemistry
Atom and Molecular Physics and Optics
Condensed Matter Physics
DOI
10.1021/acs.inorgchem.2c01190
PubMed
35881069