联苯甲酰修饰β-CD构建钍、铀酰金属配合物及其吸附研究

发布时间：2018-04-04 15:54

  本文选题：β-环糊精包合物　切入点：Th(Ⅳ)　出处：《南华大学》2016年硕士论文

【摘要】：环糊精(CD)作为一种天然无污染的高分子有机化合物,目前,在各个领域都有非常重要的应用。尽管如此,但是天然的环糊精也存在一些缺点。因此,对天然环糊精进行改性(化学修饰)至关重要。经过化学修饰可以制备出很多种类的环糊精衍生物,这些衍生物的物理和化学性质都能得到相应的改善。β-CD作为常见的环糊精(α、β和λ三种)中应用范围最广的一种环糊精,因为其疏水性内腔的尺寸与很多分子尺寸相匹配,加上该内腔能通过疏水作用力、静电作用力、范德华力和氢键等作用力选择性地识别包合结构性能相匹配的客体分子形成包合物,而这些包合物的很多方面的性能都优于天然β-CD。因此,对β-CD的研究一直都是国内外科研工作者的研究重点。本课题的主要目标是制备出一种新型的β-CD包合物,即β-CD-6-OTs/联苯甲酰包合物,同时对其吸附性能进行考察。论文的主要部分包括以下五个方面:1.对β-CD及其衍生物进行简单概况,同时也对β-CD包合物的常见合成方法及其应用进行总结,最后提出了本课题的主要研究内容。2.采用非均相合成的方法制备出6-对甲苯磺酰酯-β-CD(β-CD-6-OTs),利用红外光谱,核磁共振氢谱和综合热分析等手段进行表征。实验结果表明,该方法简单可靠,制备的β-CD-6-OTs可作为合成下一步产物的原料。3.采用共沉淀法合成βOTs-6-CD-/联苯甲酰包合物,先利用红外光谱对其合成进行初步表征,再利用紫外可见分光光度计对联苯甲酰与β-CD-6-OTs的结合性能进行探究,采用综合热分析仪对其热稳定性进行分析,最后利用核磁共振氢谱和元素分析对其进行表征。结果表明,该方法科学合理,β-CD-6-OTs对联苯甲酰的包合效果优异,且包合常数高达95.49%。4.以β-CD-6-OTs/联苯甲酰包合物为吸附剂,对Th(Ⅳ)离子进行吸附研究。先利用红外光谱和扫描电镜等手段对吸附Th(Ⅳ)离子前后的吸附剂进行表征,再考察吸附剂在不同反应时间t、不同p H值、不同初始浓度的Th(Ⅳ)溶液C_0、不同温度T以及各种干扰离子存在条件下,对Th(Ⅳ)离子的吸附影响情况。通过一系列的单因素实验结果可知,在最佳吸附条件下,即t=20 min,pH=3.0,C_0=20mg/L,吸附剂β-CD-6-OTs/联苯甲酰包合物对Th(Ⅳ)离子的吸附情况最好,吸附平衡时的最大吸附容量Q_m=17.83g/mg,吸附率为87.8%。同时,在Mg~(2+),Pb~(2+),Zn~(2+),Fe~(3+),Cd~(2+)等5种干扰离子存在下,吸附剂仍能有效吸附Th(Ⅳ)离子。另外,吸附剂对Th(Ⅳ)离子的吸附过程符合吸附动力学和热力学模型,pH=3的HNO_3能有效脱附Th(Ⅳ)离子,且回收率高达99.2%。5.除了考察吸附剂对Th(Ⅳ)离子的吸附情况外,还将其应用于另一种具有放射性的U(Ⅵ)离子的吸附研究。同样,先利用红外光谱和扫描电镜等手段对吸附U(Ⅵ)离子前后的吸附剂进行表征,再考察吸附剂在不同反应时间t、不同p H值、不同初始浓度的U(Ⅵ)溶液C0、不同温度T以及各种干扰离子存在条件下,对U(Ⅵ)离子的吸附影响情况。由吸附实验结果可知,当=min60t,4.5p H=,mg/L20C0=时,吸附剂β-CD-6-OTs/联苯甲酰包合物对U(Ⅵ)离子的最大吸附容量g/mg16.12Qm=,吸附率为91.2%。同时,当2+Mg,3+e F,2+Cu,2+n M和2+bP的浓度￡L/mg15C时,吸附剂对U(Ⅵ)离子的吸附不受影响。另外,通过吸附动力学模型可知,准二级动力学速率方程更适合描述吸附过程,即发生的主要是化学吸附过程。通过比较Langmuir等温吸附模型(0.9907=R2)和Freundlich等温吸附模型(0.9810=R2)的模型参数可知,吸附剂对U(Ⅵ)离子的吸附过程更适合于用Langmuir等温吸附模型来描述,即吸附剂对U(Ⅵ)离子是单分子层的吸附,吸附主要发生在其表面。吸附热力学模型表明,吸附剂对U(Ⅵ)离子的吸附是自发吸热的过程。同时,8 m L 0.4mol/L的HCl能有效脱附U(Ⅵ)离子,且回收率高达99.1%。本课题为U(Ⅵ)离子的吸附提供部分参考价值。
[Abstract]:Cyclodextrin (CD) as a kind of natural macromolecule organic compound, no pollution at present, have very important applications in various fields. However, natural cyclodextrins but there are also some disadvantages. Therefore, the natural cyclodextrin modified (chemical modification) is essential. After chemical modification can be prepared out of many kinds of cyclodextrin derivatives, the physical and chemical properties of these derivatives can be improved. As a common -CD beta cyclodextrin (alpha, beta and lambda three) a cyclodextrin in the most widely used, because of its hydrophobic cavity size and many molecular size matched with the cavity through hydrophobic interaction, electrostatic force, van Edward guest molecules and hydrogen bonding force of selective recognition of inclusion structure to match the performance of clathrate formation, and the inclusion of a lot of performance is superior to the natural So the study of beta beta -CD., -CD has always been the research focus of domestic and foreign researchers. The main purpose of this research is to prepare a new type of beta -CD complexes, namely -CD-6-OTs/ beta bibenzoyl inclusion complexes, and to study its adsorption properties. The main part of the thesis includes the following five a: 1. of beta -CD and its derivatives were introduced in brief, and also summarizes the common synthesis method of beta -CD package complexes and its application, and finally put forward the method of non homogeneous synthesized 6- p-toluenesulfonyl ester beta -CD with the main research content of the subject.2. (P -CD-6-OTs). By using IR, 1H NMR and thermal analysis were characterized. The experimental results show that this method is simple and reliable, the preparation of beta -CD-6-OTs can be used as the material of the next product synthesis by.3. clathrate coprecipitation synthesis of OTs-6-CD-/ bibenzoyl, First, the synthesis preliminarily characterized by infrared spectroscopy, using UV spectrophotometer and antithetical couplet benzoyl beta -CD-6-OTs binding properties of the integrated thermal analyzer to analyze the thermal stability, characterized by 1H NMR and elemental analysis. The results show that the method is scientific reasonable, beta -CD-6-OTs antithetical couplet benzoyl inclusion effect is excellent, and the inclusion constants up to 95.49%.4. complexes as adsorbent to -CD-6-OTs/ beta bibenzoyl package of Th (IV) adsorption of ions. By infrared spectroscopy and scanning electron microscopy on the adsorption of Th (IV) before and after ion adsorbent characterization the re inspection, the adsorbent in the different reaction time of T and P in different H value, different initial concentration of Th (IV) C_0 solution, different temperature T and various interfering ions under the condition of Th (IV) adsorption effect of ions through. 涓，

本文编号：1710651