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水合肼以其碱性及吸附性受到越来越多的关注,同时它在粘土中的污染问题也越来越受到重视.本工作构建了高岭石团簇模型为Al6Si6O42H42并在B3LYP/6-31G(d,p),MP2/6-31G(d,p)//B3LYP/6-31G(d,p)和MP2/6-31++G(d,p)//B3LYP/6-31G(d,p)水平下对一水合肼以及二水合肼在高岭石层间的插层性质(如:优化构型、结构参数、结合能、电荷分布、振动光谱、静电势等)进行探究.计算表明,当一水合肼进入层间后,水分子和肼分子之间的相互作用发生了改变.即水与肼分子分别以氢键的形式插层于高岭石层间,且肼与高岭石之间的相互作用要强于肼与水之间的相互作用,同时插层位点多位于高岭石四面体层和八面体层的重叠区域内,这些都是水合肼易进入高岭石层间而难以脱去的重要因素.当二水合肼进入层间后,随着层间距的不断扩大,肼分子与高岭石铝氧层之间的相互作用仍强于肼分子与水分子间的作用.但当层间距超过1.05 nm时,水分子与肼分子之间的作用则强于肼分子与高岭石的作用,这也印证了若要将肼脱附,需将层间距增大以减弱肼分子与高岭石的作用,再用溶剂将其脱附的可行性.
Hydrazine hydrate is paid more and more attention due to its alkalinity and adsorbability.At the same time, hydrazine hydrate is paid more and more attention in the clay. In this work, the kaolinite cluster model was Al6Si6O42H42, (D, p), MP2 / 6-31G (d, p) // B3LYP / 6-31G (d, p) and MP2 / 6-31 ++ G (d, p) // B3LYP / 6-31G (d, p) of hydrazine hydrate and hydrazine hydrate in the intercalation of kaolinite interlayer properties (such as: the optimal configuration, structure parameters, binding energy, charge distribution, vibrational spectra, electrostatic potential, etc.) to explore The calculations show that when the hydrazine monohydrate enters the interlayer, the interaction between water molecules and hydrazine molecules changes, that is, the water and hydrazine molecules interpenetrate in the form of hydrogen bonds between the kaolinite layers, respectively, and the hydrazine and The interaction between kaolinite is stronger than the interaction between hydrazine and water, while the intercalation sites are mostly located in the overlapping region of kaolinite tetrahedron and octahedron, which are easily accessible to hydrazine hydrate Rock layer and difficult to take off an important factor.When hydrazine hydrate into the interlayer, with the continuous expansion of the layer spacing, hydrazine molecules and the interaction between the kaolinite alumina layer is still stronger than the hydrazine molecules and water molecules between However, when the distance between layers exceeds 1.05 nm, the interaction between water molecules and hydrazine molecules is stronger than that between hydrazine molecules and kaolinite, which confirms that if the hydrazine is desorbed, the interlayer spacing needs to be increased Weaken the role of hydrazine molecules and kaolinite, and then the solvent desorption feasibility.