Creating Reactivity with Unstable Endmembers using Pressure and Temperature: Synthesis of Bulk Cubic Mg<sub>0.4</sub>Fe<sub>0.6</sub>N

Serghiou, George; Ji, Gang; Odling, Nicholas; Reichmann, H. J.; Morniroli, J. P.; Boehler, Reinhard; Frost, D. J.; Wright, Jonathan P.; Wunder, Bernd

doi:10.1002/ange.201506257

Cited by 4 publications

(2 citation statements)

References 44 publications

(26 reference statements)

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“…After the HPHT reaction, LaN-1/3NaN 3 (nominally La 1− x Na 3 x N with x = 0.10) and LaN-1/2NaN 3 ( x = 0.14) samples were found to contain a single tetragonal phase with a rocksalt-related structure and cell parameters a≈ac/2 and c ≈ a c where c<2a. This is different to the only previously reported tetragonal form of LaN where the lattice distortion has c>2a [15] and the X-ray patterns also do not match those of known high-pressure LaN or NaN 3 or Na 3 N phases [26–29].…”

Section: Resultsmentioning

confidence: 61%

“…Decomposition of NaN 3 results both in a high nitrogen activity and metallic Na to act as a flux, but there is the possibility that Na could be incorporated into a product phase. No Na was found within the latter materials or other reported products of HPHT reactions with NaN 3 such as rocksalt-type Mg 0.4 Fe 0.6 N [15], but we have investigated this possibility through HPHT reactions of NaN 3 with the simple nitride LaN to discover whether ternary Na-containing products can be formed.…”

Section: Introductionmentioning

confidence: 99%

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Defect rocksalt structures in the La-Na-N system

Yuan,

Kloß,

Attfield

2023

Phil. Trans. R. Soc. A.

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Sodium azide (NaN 3 ) is a versatile nitrogen source that can be used for the synthesis of new nitrides under high-pressure and temperature conditions. Reactions between lanthanum nitride (LaN) and sodium azide (NaN 3 ) at 800°C under 8 GPa pressure have led to the discovery of two defect rocksalt phases which are the first reported ternaries in the La-Na-N system. Preliminary structure assignments have been made based on fits to powder X-ray diffraction profiles. One phase is La 1− x Na 3 x N with vacancies at octahedral La sites and interstitial tetrahedral Na cations. This phase has a tetragonally distorted rocksalt structure (space group I 4 / mmm , a = 3.8704(2) and c = 5.2098(3) Å for nominal x = 0.10) and the distortion decreases with increasing Na content (space group I 4 / mmm , a = 3.8060(2) Å, c = 5.2470(3) Å for nominal x = 0.14), further giving a cubic phase ( a = 5.3055(2) Å) for nominal x = 0.25. This coexists with another cubic F m 3 ¯ m phase ( a = 5.1561 (5) Å), tentatively identified as rocksalt ‘NaN 1/3 ’ stabilized by a small amount of La; NaLa y N (1+3 y )/3 with y ≈ 1%. These initial investigations reveal that the high-pressure La-Na-N phase diagram may be rich in defect rocksalt-type materials although further work using neutron diffraction will be needed to confirm the structures. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

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Section: Resultsmentioning

confidence: 61%

Section: Introductionmentioning

confidence: 99%

Defect rocksalt structures in the La-Na-N system

Yuan,

Kloß,

Attfield

2023

Phil. Trans. R. Soc. A.

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Preparation of Bulk‐Phase Nitride Perovskite LaReN₃ and Topotactic Reduction to LaNiO₂‐Type LaReN₂

2021

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While halide and oxide perovskites are numerous and many display outstanding properties, ABN3 perovskite nitrides are extremely rare due to synthetic challenges arising from the low chemical potential of nitrogen and a tendency to form low‐coordination nitridometallate anions. We report the preparation of a perovskite nitride LaReN3 through azide‐mediated oxidation at high pressure. High‐resolution synchrotron diffraction shows that LaReN3 has a low‐symmetry, triclinic, perovskite superstructure resulting from orbital ordering with strong spin‐orbit coupling distortions. Topotactic reduction of LaReN3 above 500 °C leads to layered tetragonal LaReN2 via a probable LaReN2.5 intermediate, which is the first reported example of nitride defect perovskites. Magnetisation and conductivity measurements indicate that LaReN3 and LaReN2 are both metallic solids. The two chemical approaches presented are expected to lead to new classes of ABN3 and defect ABN3−x nitride perovskite materials.

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Preparation of Bulk‐Phase Nitride Perovskite LaReN₃ and Topotactic Reduction to LaNiO₂‐Type LaReN₂

2021

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While halide and oxide perovskites are numerous and many display outstanding properties, ABN 3 perovskite nitrides are extremely rare due to synthetic challenges arising from the low chemical potential of nitrogen and a tendency to form low-coordination nitridometallate anions. We report the preparation of a perovskite nitride LaReN 3 through azidemediated oxidation at high pressure. High-resolution synchrotron diffraction shows that LaReN 3 has a low-symmetry, triclinic, perovskite superstructure resulting from orbital ordering with strong spin-orbit coupling distortions. Topotactic reduction of LaReN 3 above 500 8C leads to layered tetragonal LaReN 2 via a probable LaReN 2.5 intermediate, which is the first reported example of nitride defect perovskites. Magnetisation and conductivity measurements indicate that LaReN 3 and LaReN 2 are both metallic solids. The two chemical approaches presented are expected to lead to new classes of ABN 3 and defect ABN 3Àx nitride perovskite materials.

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Creating Reactivity with Unstable Endmembers using Pressure and Temperature: Synthesis of Bulk Cubic Mg_0.4Fe_0.6N

Cited by 4 publications

References 44 publications

Defect rocksalt structures in the La-Na-N system

Defect rocksalt structures in the La-Na-N system

Preparation of Bulk‐Phase Nitride Perovskite LaReN₃ and Topotactic Reduction to LaNiO₂‐Type LaReN₂

Preparation of Bulk‐Phase Nitride Perovskite LaReN₃ and Topotactic Reduction to LaNiO₂‐Type LaReN₂

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Creating Reactivity with Unstable Endmembers using Pressure and Temperature: Synthesis of Bulk Cubic Mg0.4Fe0.6N

Cited by 4 publications

References 44 publications

Defect rocksalt structures in the La-Na-N system

Defect rocksalt structures in the La-Na-N system

Preparation of Bulk‐Phase Nitride Perovskite LaReN3 and Topotactic Reduction to LaNiO2‐Type LaReN2

Preparation of Bulk‐Phase Nitride Perovskite LaReN3 and Topotactic Reduction to LaNiO2‐Type LaReN2

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Creating Reactivity with Unstable Endmembers using Pressure and Temperature: Synthesis of Bulk Cubic Mg_0.4Fe_0.6N

Preparation of Bulk‐Phase Nitride Perovskite LaReN₃ and Topotactic Reduction to LaNiO₂‐Type LaReN₂

Preparation of Bulk‐Phase Nitride Perovskite LaReN₃ and Topotactic Reduction to LaNiO₂‐Type LaReN₂