Pressure-stabilized hafnium nitrides and their properties

Zhang, Jin; Oganov, Artem R.; Li, Xinfeng; Niu, Haiyang

doi:10.1103/physrevb.95.020103

Cited by 102 publications

(128 citation statements)

References 46 publications

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“…À units were recently reported in CuN 2 at high pressure. [34] The framework HfN 8 •N 2 , isostructural to WN 8 •N 2 and ReN 8 •N 2 , was previously predicted by Zhang et al [22] The absence of this topology among the Hf compounds we observed in our experiments may have the following explanation. First, whereas WN 8 obeys the 18e rule and ReN 8 , as a 19e complex, shows just a small deviation, the HfN 8 framework would have been a less stable 16e complex (the same reasoning could also explain why Os does not form a 20e OsN 8 complex).…”

Section: Angewandte Chemiesupporting

confidence: 75%

“…[16] Polydiazenediyl chains are also theoretically predicted to exist in CaN 4 , ReN 4 , and HfN 8 •N 2 . [20][21][22][23] Along with a pentazolate anion, the polydiazenediyl chain may be one of the most stable structural units to be preserved at ambient pressures.…”

Section: Zuschriftenmentioning

confidence: 99%

“…In the search of the predicted HfN 8 •N 2 compound at lower pressures, we reheated the sample at 73 GPa. [22] The resulting material was cubic Hf 3 N 4 (I4 3d, No. 220, a = 6.2946(13) ), as evident from the SCXRD analysis (Supporting Information, Table S5).…”

Section: Angewandte Chemiementioning

confidence: 99%

See 2 more Smart Citations

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

et al. 2020

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Polynitrides are intrinsically thermodynamically unstable at ambient conditions and require peculiar synthetic approaches. Now, a one‐step synthesis of metal–inorganic frameworks Hf4N20⋅N2, WN8⋅N2, and Os5N28⋅3 N2 via direct reactions between elements in a diamond anvil cell at pressures exceeding 100 GPa is reported. The porous frameworks (Hf4N20, WN8, and Os5N28) are built from transition‐metal atoms linked either by polymeric polydiazenediyl (polyacetylene‐like) nitrogen chains or through dinitrogen units. Triply bound dinitrogen molecules occupy channels of these frameworks. Owing to conjugated polydiazenediyl chains, these compounds exhibit metallic properties. The high‐pressure reaction between Hf and N2 also leads to a non‐centrosymmetric polynitride Hf2N11 that features double‐helix catena‐poly[tetraz‐1‐ene‐1,4‐diyl] nitrogen chains [−N−N−N=N−]∞.

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Section: Angewandte Chemiesupporting

confidence: 75%

Section: Zuschriftenmentioning

confidence: 99%

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High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

et al. 2020

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“…Notably, the zeta phase has been experimentally observed to form in the V‐C, Nb‐C, Hf‐N and Ta‐N systems . Computationally, the stoichiometric zeta phase was found to lie only on the convex hull of the Hf‐N system, that is ζ‐Hf 4 N 3 . However, the experimental studies of these compounds suggest that the zeta phase is sub‐stoichiometric at roughly the M 3 X 2 composition.…”

Section: Resultsmentioning

confidence: 95%

A computational search for the zeta phase in the tantalum carbides

Weinberger

Thompson

2018

J Am Ceram Soc

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A systematic electronic structure density functional theory search for the zeta phase in the tantalum carbon system has been conducted, demonstrating that the zeta phase does indeed lie on the convex hull, establishing low‐temperature thermodynamic stability, and is structurally stable. Even though the zeta phase is most oft reported as a R3¯m ζ‐Ta4C3‐x structure, these new computational results reveal that the perfectly ordered zeta phase occurs at the Ta3C2 composition and belongs to the C2/m space group. Furthermore, these results suggest that the R3¯m space group may be a result of an order‐disorder transition and potential deviations from ideal stoichiometry at higher temperatures. The structure of this Ta3C2 compound can be described as ordered strings of carbon vacancies on a single carbon plane, which is also the preferred plane where additional carbon vacancies or interstitials form. These defects have modest formation energies, which provides further explanation for the small homogeneity range in zeta phase.

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“…Recently synthesized MgN 4 featuring polydiazenediyl chains could be even recovered at ambient conditions . Polydiazenediyl chains are also theoretically predicted to exist in CaN 4 , ReN 4 , and HfN 8 ⋅N 2 . Along with a pentazolate anion, the polydiazenediyl chain may be one of the most stable structural units to be preserved at ambient pressures.…”

Section: Figurementioning

confidence: 99%

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

et al. 2020

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Pressure-stabilized hafnium nitrides and their properties

Cited by 102 publications

References 46 publications

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

A computational search for the zeta phase in the tantalum carbides

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

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Pressure-stabilized hafnium nitrides and their properties

Cited by 102 publications

References 46 publications

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf4N20⋅N2, WN8⋅N2, and Os5N28⋅3 N2 with Polymeric Nitrogen Linkers

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf4N20⋅N2, WN8⋅N2, and Os5N28⋅3 N2 with Polymeric Nitrogen Linkers

A computational search for the zeta phase in the tantalum carbides

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf4N20⋅N2, WN8⋅N2, and Os5N28⋅3 N2 with Polymeric Nitrogen Linkers

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High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers