High-Pressure Synthesis of the β-Zn₃N₂ Nitride and the α-ZnN₄ and β-ZnN₄ Polynitrogen Compounds

Titelangaben

Laniel, Dominique ; Aslandukova, Alena ; Aslandukov, Andrii ; Fedotenko, Timofey ; Chariton, Stella ; Glazyrin, Konstantin ; Prakapenka, Vitali B. ; Dubrovinsky, Leonid ; Dubrovinskaia, Natalia:
High-Pressure Synthesis of the β-Zn₃N₂ Nitride and the α-ZnN₄ and β-ZnN₄ Polynitrogen Compounds.
In: Inorganic Chemistry. Bd. 60 (2021) Heft 19 . - S. 14594-14601.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.1c01532

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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: β-Zn3N2, α-ZnN4, and β-ZnN4, formed at 35.0, 63.5, and 81.7 GPa, respectively. Whereas β-Zn3N2 contains the N3– nitride, both ZnN4 solids are found to be composed of polyacetylene-like [N4]∞2– chains. Upon the decompression of β-ZnN4 below 72.7 GPa, a first-order displacive phase transition is observed from β-ZnN4 to α-ZnN4. The α-ZnN4 phase is detected down to 11.0 GPa, at lower pressures decomposing into the known α-Zn3N2 (space group Ia3̅) and N2. The equations of states of β-ZnN4 and α-ZnN4 are also determined, and their bulk moduli are found to be K0 = 126(9) GPa and K0 = 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.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: β-Zn3N2, α-ZnN4, and β-ZnN4, formed at 35.0, 63.5, and 81.7 GPa, respectively. Whereas β-Zn3N2 contains the N3– nitride, both ZnN4 solids are found to be composed of polyacetylene-like [N4]∞2– chains. Upon the decompression of β-ZnN4 below 72.7 GPa, a first-order displacive phase transition is observed from β-ZnN4 to α-ZnN4. The α-ZnN4 phase is detected down to 11.0 GPa, at lower pressures decomposing into the known α-Zn3N2 (space group Ia3̅) and N2. The equations of states of β-ZnN4 and α-ZnN4 are also determined, and their bulk moduli are found to be K0 = 126(9) GPa and K0 = 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.