【作者】 张楠；

【导师】 李蕾；

【作者基本信息】 北京化工大学 ， 物理化学， 2006， 硕士

【摘要】 本论文主要以镁铝、镁铁及锌铝水滑石为主体，丁烯二酸异构体(顺丁烯二酸和反丁烯二酸)为有机阴离子客体，采用离子交换法研究了水滑石类层状化合物与丁烯二酸异构体阴离子的插层反应。采用XRD、IR和TG等表征手段分析了插层所得产物的晶体结构特征。研究表明：镁铝水滑石和锌铝水滑石在各溶剂中对丁烯二酸异构体阴离子都存在明显的插层选择性，反丁烯二酸比顺丁烯二酸优先进入层间，各种表征结果说明插层产物具有较好的晶体结构；而镁铁水滑石难以与客体进行离子交换，且在反应中层板容易破坏。 本论文还采用Gaussian-98软件包中的ab initio分子轨道法(HF／6-31G)计算了顺反丁烯二酸异构体阴离子的分子结构，并结合实验数据从微观作用的角度分析了LDHs体系插层过程中主体与客体的相互作用，从而确定插层过程中的选择性的影响规律及插层机理。结果表明，LDHs对丁烯二酸异构体阴离子的插层选择性与该阴离子的氧原子的电荷布居、空间构型、偶极距密切相关，从理论上揭示了反丁烯二酸比顺丁烯二酸容易进入水滑石层间的可能原因。 此外，论文还考察了温度、溶剂和混合酸溶液配比等因素对插层选择性的影响。结果表明，在水溶液中，对Mg-Al LDHs体系，反应温度可影响插层选择性，温度低于40℃时，顺丁烯二酸反应量大于反丁烯二酸，更多还原

【Abstract】 In this thesis, intercalation of cis-but-2-enedioate anion or trans -but-2-enedioate anion into the layered double hydroxides (Mg-Al LDHs, Mg-Fe LDHs and Zn-Al LDHs) was carried out by the method of ion-exchange procedures. Selective reaction was observed in competitive experiments involving an equal concentration pairs of acids. The trans -but-2-enedioate anion is preferentially intercalated into the Mg-Al LDHs and Zn-Al LDHs. However, but-2-enedioate anions are hardly intercalated into the Mg-Fe LDHs and the layered structure of Mg-Fe LDHs is easily destroyed during the ion-exchange process.The obtained intercalation compounds were characterized by X-ray diffraction, infrared and thermogravimetry techniques. The charge density on the oxygens of each of the carboxylate groups for both anions was investigated utilizing ab initio (HF/6-31G) method by Gaussian-98. Combined with the experimental data, the guest size and the charge density of the oxygens of the guest, the orientation of both anions between the layers was更多还原