Frost Ray L, Kristof János, Kloprogge J Theo, Horvath Erzsébet
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, G.P.O. Box 2434, Brisbane, Queensland 4001, Australia.
J Colloid Interface Sci. 2002 Feb 1;246(1):164-74. doi: 10.1006/jcis.2001.8011.
The deintercalation of hydrazine-intercalated kaolinite has been followed using a combination of X-ray diffraction and diffuse reflectance Fourier transform infrared spectroscopy. Upon intercalation of the kaolinite with hydrazine, the kaolinite layers are expanded to 10.66 A and remain expanded for up to 22 h upon exposure to moist air. Only upon deintercalation are the peak at 10.39 A and a minor peak at 9.6 A observed. Complete deintercalation takes up to 18 days more. Upon intercalation with hydrazine an intense band is observed at 3628 cm(-1) and is attributed to the inner-surface hydroxyls hydrogen bonded to the hydrazine, which upon deintercalation decreased in intensity. This rate of deintercalation is affected by the presence or absence of moist air. Deintercalation in the presence of water vapor results in the observation of two additional bands at 3550 and 3598 cm(-1), which are attributed to the hydroxyl stretching modes of adsorbed water during deintercalation. The intensity of NH stretching vibrations observed at 3360, 3300, and 3200 cm(-1) also decrease in intensity with deintercalation time. Changes in the hydroxyl deformation modes of kaolinite in the 915 cm(-1) region and in the HNH deformation modes show strong interactions between the kaolinite surface and the inserting hydrazine molecule.
采用X射线衍射和漫反射傅里叶变换红外光谱相结合的方法,对肼插层高岭土的脱插层过程进行了跟踪研究。高岭土与肼插层后,高岭土层间距扩大到10.66 Å,在暴露于潮湿空气中时,这种扩张状态可持续长达22小时。只有在脱插层时,才会观察到10.39 Å处的峰和9.6 Å处的一个小峰。完全脱插层需要长达18天的时间。与肼插层时,在3628 cm⁻¹处观察到一个强吸收带,这归因于与肼形成氢键的内表面羟基,脱插层时该吸收带强度降低。这种脱插层速率受潮湿空气存在与否的影响。在水蒸气存在下脱插层会观察到另外两个位于3550和3598 cm⁻¹处的吸收带,这归因于脱插层过程中吸附水的羟基伸缩振动模式。在3360、3300和3200 cm⁻¹处观察到的NH伸缩振动强度也随脱插层时间而降低。高岭土在915 cm⁻¹区域的羟基变形模式以及HNH变形模式的变化表明高岭土表面与插入的肼分子之间存在强烈的相互作用。