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羟基氧化铁钾KFeO(OH)：水热合成、化学与热不稳定性、晶体与磁结构

Oxo-Hydroxoferrate K FeO (OH) : Hydroflux Synthesis, Chemical and Thermal Instability, Crystal and Magnetic Structures.

作者信息

Albrecht Ralf, Hunger Jens, Block Theresa, Pöttgen Rainer, Senyshyn Anatoliy, Doert Thomas, Ruck Michael

机构信息

Faculty of Chemistry and Food Chemistry TU Dresden 01062 Dresden Germany.

Institut für Anorganische und Analytische Chemie WWU Münster Corrensstraße 30 48149 Münster Germany.

出版信息

ChemistryOpen. 2019 Jan 24;8(1):74-83. doi: 10.1002/open.201800229. eCollection 2019 Jan.

DOI:10.1002/open.201800229
PMID:30693170
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6345222/
Abstract

The reaction of Fe(NO)⋅9 HO with KOH under hydroflux conditions at about 200 °C produces red crystals of K FeO (OH) in a quantitative yield. In the crystal structure, edge-sharing [FeO] octahedra form FeO] honeycomb nets. Pillars consisting of pairs of vertex-sharing [FeO] tetrahedra link the honeycomb layers and form columnar halls in which the potassium ions are located. The trigonal ( 1) and the hexagonal (6/) polytypes of K FeO (OH) show oriented intergrowth. The sub-stoichiometric potassium content (≈0.3) is compensated by hydroxide ions. K FeO (OH) is an antiferromagnet above 2 K and its magnetic structure was determined by neutron powder diffraction. Under ambient conditions, K FeO (OH) hydrolyzes and KCO ⋅ HO forms gradually on the surface of the K FeO (OH) crystals. Upon annealing at air at about 500 °C, the potassium atoms in the columnar halls start to order into a superstructure. The thermal decomposition of K FeO (OH) proceeds via a topotactic transformation into K FeO, adopting the rhombohedral β'' or the hexagonal β-aluminate-type structure, before γ-FeO is formed above 950 °C, which then converts into thermodynamically stable α-FeO.

摘要

在约200°C的水热条件下，Fe(NO)⋅9H₂O与KOH反应以定量产率生成K₂FeO(OH)₂的红色晶体。在晶体结构中，共边的[FeO]八面体形成[Fe₂O]蜂窝状网络。由成对的共顶[FeO]四面体组成的柱连接蜂窝层并形成柱状空间，钾离子位于其中。K₂FeO(OH)₂的三方(1)和六方(6/)多型显示出定向共生。亚化学计量的钾含量(≈0.3)由氢氧根离子补偿。K₂FeO(OH)₂在2K以上是反铁磁体，其磁结构由中子粉末衍射确定。在环境条件下，K₂FeO(OH)₂水解，K₂CO₃⋅H₂O在K₂FeO(OH)₂晶体表面逐渐形成。在约500°C的空气中退火时，柱状空间中的钾原子开始有序排列成超结构。K₂FeO(OH)₂的热分解通过拓扑转变为K₂Fe₂O₄进行，采用菱面体β''或六方β-铝酸盐型结构，在950°C以上形成γ-Fe₂O₃，然后转变为热力学稳定的α-Fe₂O₃。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/870d6b1998f0/OPEN-8-74-g014.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/785e7c89d5ad/OPEN-8-74-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/eb8a9b6be256/OPEN-8-74-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/2a0d3a065a3c/OPEN-8-74-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/5f734bf50ede/OPEN-8-74-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/c4a5a0641964/OPEN-8-74-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/e666c2cad3f1/OPEN-8-74-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/09092e8da8a9/OPEN-8-74-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/870d6b1998f0/OPEN-8-74-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/6fe592195a4d/OPEN-8-74-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/3899298207f4/OPEN-8-74-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/313edde36b93/OPEN-8-74-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/b170c2d6628f/OPEN-8-74-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/34c86c526d92/OPEN-8-74-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/9e04db4dc566/OPEN-8-74-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/785e7c89d5ad/OPEN-8-74-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/eb8a9b6be256/OPEN-8-74-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/2a0d3a065a3c/OPEN-8-74-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/5f734bf50ede/OPEN-8-74-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/c4a5a0641964/OPEN-8-74-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/e666c2cad3f1/OPEN-8-74-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/09092e8da8a9/OPEN-8-74-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a1b4/6345222/870d6b1998f0/OPEN-8-74-g014.jpg

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本文引用的文献

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