摘要
随着国民经济的日益发展,人们对纳米材料的性能提出了更高的要求,具有多功能性的磁性纳米复合材料便应运而生。近年来,人们通过对材料性能的设计,开发了多种新型的磁性纳米复合材料,其中具有核壳结构的磁性纳米复合材料是较为突出的一类。本文以水滑石类化合物(LDHs)为壳层,以具有强磁性的四氧化三铁(Fe304)为核,通过一步共沉淀法制备出了具有典型核壳结构的磁性纳米复合材料。通过对磁性复合材料的结构和性能研究,来进一步揭示它们之间的联系,并为开发类似结构的复合材料提供一种新方法和新思路。本文的主要研究内容和创新点如下：
(1)采用修饰了的溶剂热法,通过调控起始溶液中的[Fe3+]制备不同尺寸的Fe304纳米粒。通过XRD、SEM/TEM及VSM表征表明,合成出了球形、近单分散分布并具有强的比饱和磁化强度的200 nm和500 nm的Fe304纳米颗粒。
(2)以500 nm的Fe304为磁核,以具有催化活性的碳酸根插层铜镁铝水滑石(CuMgAl-LDH)为壳,通过对制备方法的选择以及条件优化,成功制备出了具有典型核@壳结构的Fe3O4@CuMgAl-LDH磁性纳米催化剂。其粒子大小约为550 nm,水滑石壳层厚度约为50nm,比饱和磁化强度为53.69 emu/g。低温N2吸脱附曲线呈现出明显的滞后环,说明该复合材料具有丰富的孔道结构。通过对得到的磁性纳米催化剂在不同温度下焙烧,可以得到系列衍生催化剂Fe3O4@CMAO。
苯酚羟化试验表明,与相关参比催化剂比较,在优化条件下(温度：65℃,时间：40 min,苯酚与催化剂的质量比为34),Fe3O4@CuMgAl-LDH具有最高的催化活性。苯酚的转化率和H202的有效利用率分别为47.2%和45.3%。而且,在外加磁场下该催化剂可实现方便的分离与再利用,其三次转化率均保持在38%以上,回收催化剂的晶体结构和核壳结构仍保持。Fe3O4@CuMgAl-LDH的高活性可归因于催化剂的核@壳结构,使得核与壳之间可以产生电子传递所致。XPS表明CuMgAl-LDH与Fe304之间可能主要通过Mg-O-Fe, Cu-O-Fe键的形式结合并给出了该磁性催化剂在苯酚羟化反应中的催化机理模型。
(3)以尺寸为200 nm的Fe304为磁核,以正硅酸乙酯(主要成分为二氧化硅)作为荧光物质量子点(QDs) CdSe/ZnS与磁核Fe304的连接层,以具有缓释功能的布洛芬插层镁铝水滑石(IBU-LDH)为壳,利用双滴共沉淀法成功制备出了集磁性、荧光以及药物缓释为一体的复合材料Fe3O4-SiO2-QDs-SiO2@IBU-LDH,其粒子尺寸约为240 nm左右,其中磁核约在200 nm左右,二氧化硅中间层的厚度约为20nm, CdSe/ZnS处于硅烷偶联剂和二氧化硅层之间,IBU-LDH的厚度在10 nm左右,其比饱和磁化强度为4.43 emu/g,荧光发射峰的中心峰位为607 nm。这些结果表明LDH基核壳型磁性荧光纳米载药粒子在磁靶向药物传输系统中具有潜在的应用前景。
With increasing development of the national economy, the versatility of magnetic nanocomposites has aroused wide interest owing to their their special physical and chemical properties. Recently, researchers have prepared a variety of magnetic nanocomposites with specific features, and among the magnetic nanocomposites, the core-shell structured magnetic ones are attracted more interests. In this paper, the core-shell structured magnetic nanocomposites have been successfully prepared involving a Fe3O4 core and a layered double hydroxide shell. We discuss the relationship between the structure and the properties and provide a new vision and new ideas for studying the core-shell structure magnetic nanocomposites. The main contents and innovations are as follows:
(1) The magnetic Fe3O4 nanoparticles with different diameters (ca. 200 nm and 500 nm) were prepared by a solvothermal reaction via modulating the initial concentration of [Fe3+] and characterized by XRD, SEM and VSM techniques. The obtained magnetic nanoparticles present spherical and nearly uniform morphology with strong saturation magnetization.
(2) A well-defined core-shell structured magnetic nanocatalyst of Fe3O4@CuMgAl-LDH was fabricated via optimizing preparation method and conditions. The prepared nanocomposites presents well-defined core-shell structure involving CuMgAl-LDH coating of ca.50 nm onto the 500 nm Fe3O4core and strong magnetism as 53.69 emu/g. The low temperature N2 adsorption-desorption curve shows an obvious hysteresis loop, indicating that the nanocomposite material has a rich pore structure.
The obtained Fe3O4@CuMgAl-LDH nanocomposites was employed in phenol hydroxylation by H2O2 and exhibits high catalytic activity compared with other related catalysts. Under optimal reaction condition the phenol conversion and the efficiency of H2O2 reaches 47.2% and 45.3% over Fe3O4@CuMgAl-LDH, respectively. Moreover after separrtion with a external magnetic field, the activity of the recycled catalyst nearly preserves its initial activity and the basic structure of it unchanged. The mechnism of the phenol hydroxylation and relationship between the core and the shell are discussed base on the H2-TPR and XPS. We proposed that the Fe3O4 core and the CuMgAl-LDH shell are linked via the bond of Cu-O-Fe and Mg-o-Fe. Fe3O4@CMAO at diffierent calcined temperature are obtained by calcined the Fe3O4@CuMgAl-LDH at different temperatures.
(3) The magentic fluorescent nanocomposites Fe3O4-SiO2-QDs-SiO2 @IBU-LDH are succsessfully synthesised by coprecipitation method. The obtained nanocomposites presents well-defined core-shell structure involving IBU-LDH coating of ca.10 nm onto the 230 nm Fe3O4 core modified by silica and quantum dots with a silica intermediate layer thickness about 20 nm and strong magnetism as 4.43 emu/g. These results show that the LDH-based core-shell fluorescent magnetic nanoparticles in magnetic targeting drug-loaded drug delivery system has potential applications.
引文
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