γ-FeO(OH)(s)结构类型的研究及与Cu(OH)2(s)结构的比较

Yannick Cudennec, André Lecerf
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引用次数: 8

摘要

对Cu(OH)2(s)和γ-FeO(OH)(s)的晶体结构进行比较,发现两种固相虽然分子式不同,但结构相似。这种类比与多面体相似的连接模式有关,多面体产生由波浪片组成的二维结构。从二价氢氧化铁Fe(OH)2(s)中得到γ-FeO(OH)(s),其也呈现水镁石型二维骨架。我们提出了这种反应的一种机制,它可能是拓扑的。与水镁石类型相反,由此产生的鳞石结构类型允许八面体阳离子配位的强烈变形。变形可能是由于γ-FeO(OH)(s)中氢原子的损失或Cu(OH)2(s)中影响二价铜的强Jahn-Teller效应。如果氢氧化铜不能像对铁(OH)2(s)那样与水镁石形成同构关系,那么就存在与鳞绿石的类似关系,即使铜的周围是五面体,而不是三价铁的八面体。在这两种晶体结构中,一个氧原子都有一个由两个阳离子和一个氢原子组成的特殊环。这一特征可能解释了这种结构类型的低稳定性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Étude du type structural de γ-FeO(OH)(s) et comparaison avec la structure de Cu(OH)2(s)

Comparison of the crystal structures of Cu(OH)2(s) and γ-FeO(OH)(s) shows a structural analogy between both solid phases, despite the difference of formulas. This analogy is related to similar connection modes of the polyhedra, which give rise to two-dimensional structures composed of wavy sheets. Lepidocrocite, γ-FeO(OH)(s), is obtained from divalent iron hydroxide Fe(OH)2(s), which exhibits also a two-dimensional framework of brucite type. We propose a mechanism for this reaction, which is probably topotactic. The resulting lepidocrocite structural type allows strong deformations of the octahedral cationic coordination, contrarily to the brucite type. Deformations can be due to the loss of hydrogen atoms in γ-FeO(OH)(s) or to the strong Jahn–Teller effect that affects divalent copper in Cu(OH)2(s). If copper hydroxide cannot be isostructural with brucite as it is for Fe(OH)2(s), an analogy exists with lepidocrocite, even if copper has a pentahedral surrounding, different of that of trivalent iron, which is octahedral. In both crystal structures, one oxygen atom has a peculiar surrounding composed of only two cations and one hydrogen atom. This feature explains probably the low stability of this structural type.

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