High-Pressure Synthesis of the β-Zn3N2 Nitride and the α-ZnN4 and β-ZnN4 Polynitrogen Compounds
- 14 September 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 60 (19), 14594-14601
- https://doi.org/10.1021/acs.inorgchem.1c01532
Abstract
High-pressure nitrogen chemistry has expanded at a formidable rate over the past decade, unveiling the chemical richness of nitrogen. Here, the Zn-N system is investigated in laser-heated diamond anvil cells by synchrotron powder and single-crystal X-ray diffraction, revealing three hitherto unobserved nitrogen compounds: beta-Zn3N2, alpha-ZnN4, and beta-ZnN4, formed at 35.0, 63.5, and 81.7 GPa, respectively. Whereas beta-Zn3N2 contains the N3- nitride, both ZnN4 solids are found to be composed of polyacetylene-like [N-4](infinity)(2-) chains. Upon the decompression of beta-ZnN4 below 72.7 GPa, a first-order displacive phase transition is observed from beta-ZnN4 to alpha-ZnN4. The alpha-ZnN4 phase is detected down to 11.0 GPa, at lower pressures decomposing into the known alpha-Zn3N2 (space group Ia (3) over bar) and N-2. The equations of states of beta-ZnN4 and alpha-ZnN4 are also determined, and their bulk moduli are found to be K-0 = 126(9) GPa and K-0 = 76(12) GPa, respectively. Density functional theory calculations were also performed and provide further insight into the Zn-N system. Moreover, comparing the Mg-N and Zn-N systems underlines the importance of minute chemical differences between metal cations in the resulting synthesized phases.Keywords
Funding Information
- Bundesministerium f??r Bildung und Forschung (05K19WC1)
- Deutsche Forschungsgemeinschaft (DU 39313/1, DU 3939/2, DU 95411/1, LA-4916/1-1)
- Alexander von Humboldt-Stiftung
- Swedish Government Strategic Research Area in Materials Science on Functional Materials, Link??ping University (2009 00971)
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