Observation of Staging during Intercalation in Layered α-Cobalt Hydroxides: A Synthetic and Kinetic Study

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• 作者：Yi Du ; Dermot O’ ; Hare
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：December 15, 2008
• 年：2008
• 卷：47
• 期：24
• 页码：11839-11846
• 全文大小：499K
• 年卷期：v.47,no.24(December 15, 2008)
• ISSN：1520-510X

文摘

The anion-exchange reaction of the layered α-cobalt hydroxides Co(OH)_1.75(DDS)_0.25·0.6H₂O (1) and Co(OH)_1.7Cl_0.3·0.4H₂O (3) with carbonate has been investigated. For 3 the reaction proceeds by complete displacement of the interlayer Cl⁻ anions by CO₃²⁻ to give Co(OH)_1.7(CO₃)_0.15·0.6H₂O (4). Remarkably for 1 we only observe ion-exchange of the DDS⁻ from every other layer to give the second stage intercalate Co(OH)_1.75(DDS)_0.07(CO₃)_0.09·0.5H₂O (2). The kinetics of these processes have been investigated using time-resolved in situ energy dispersive XRD and small/wide-angle X-ray scattering. In both cases the reaction order (n) was found to be consistent with a two-dimensional diffusion controlled model. Both 3 and 4 are magnetically ordered, and dc and ac magnetic susceptibility measurements have been used to explore their 3D ferrimagnetically ordered ground states.