Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α'-P(3) N(5,) δ-P(3) N(5) and PN(2).
Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α'-P(3) N(5,) δ-P(3) N(5) and PN(2).
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DOI：
10.1002/chem.202201998
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发表时间：
2022-11-07
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非金属氮化物是一个令人兴奋的化学领域，具有大量具有出色材料性能的化合物。这些性质主要依赖于最大化强共价键的数量，交联的XN 6八面体框架特别有吸引力。在这项研究中，在激光加热的金刚石对顶砧单元中研究了高达137 GPa的磷-氮体系，合成了三种以前未观察到的相，并通过单晶X射线衍射，拉曼光谱测量和密度泛函理论计算进行了表征。 δ-P3 N5和PN 2分别在72和134 GPa下形成，并且都具有迄今为止难以捉摸的PN 6单元的密集3D网络。 这两种化合物是超不可压缩的，对于δ-P3 N5具有K 0=322 GPa的体积模量，对于PN 2具有K 0 = 339 GPa的体积模量。 在低于7 GPa的减压下，δ-P3 N5经历转变成一种新的α′-P3 N5固体，在环境条件下稳定，具有基于PN 4四面体的独特结构类型。 α′-P3 N5的形成强调了可以通过在高压下形成的材料来探索相空间。 分阶段，分阶段：在激光加热的金刚石对顶砧单元中对磷-氮体系的研究导致分别在72和134 GPa下合成新的δ-P3 N5和PN 2相 。它们的结构由PN 6八面体组成。减压后，δ-P3 N5转化为在环境条件下稳定的新型α′-P3 N5固体。
Non‐metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN6 octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser‐heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single‐crystal X‐ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ‐P3N5 and PN2 were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN6 units. The two compounds are ultra‐incompressible, having a bulk modulus of K 0=322 GPa for δ‐P3N5 and 339 GPa for PN2. Upon decompression below 7 GPa, δ‐P3N5 undergoes a transformation into a novel α′‐P3N5 solid, stable at ambient conditions, that has a unique structure type based on PN4 tetrahedra. The formation of α′‐P3N5 underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure. Phase in, phase out: Investigations of the phosphorus–nitrogen system in a laser‐heated diamond anvil cell resulted in the synthesis of new δ‐P3N5 and PN2 phases at 72 and 134 GPa, respectively. Their structures are composed of PN6 octahedra. Upon decompression, δ‐P3N5 transforms into the novel α′‐P3N5 solid that is stable under ambient conditions.
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影响因子：
1.6
作者：
Fedotenko, T.;Dubrovinsky, L.;Dubrovinskaia, N.
通讯作者：
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影响因子：
2.3
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影响因子：
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Hemley, Russell J.