一维嵌套结构柔性纳米材料的设计、构筑及光磁性能研究

One-dimensional nested structural nanomaterials are special structural nanomaterials with void space between the inner and outer layers. Nanomaterials possess a wide range of applications prospects in many fields because of their unique structures and properties. At present, the prepared methods of nested structural nanomaterials are mostly based on template-assisted means, in which the core-shell-shell composites are first synthesized by coated with multilayer shells with different materials, and then the middle layer is selectively moved by etching or calcining method. However, most of synthetic methods are complicated and may introduce some organic agents, which is not conducive to mass production. This proposal intends to use a novel technique of high-efficient combination of monoaxial electrospinning with fluorination technique to construct directly nested structural nanomaterials, including wire-in-tube structured and belt-in-hollow belt structured flexible nanomaterials. By modulating experiment parameters, structure, size and morphology of nanomaterials can be tuned. The formation mechanisms of the prepared new materials will be expounded. A novel, simple, high-efficient, universal construction techniques of these new nanostructured materials will be established. The wire-in-tube structured and belt-in-hollow belt structured flexible nanomaterials intended to be constructed in this project are based on rare earth fluorides as the core and silica as the shell. The one-dimensional nanomaterials with special structure will realize the high integration of luminescence-magnetism bifunctionality, flexibility, hydrophilia and drug loading capability. This design philosophy will provide theoretical and technical supports for constructing special structural nanomaterials.

一维嵌套结构纳米材料是在其内外层间存在空隙的特殊结构纳米材料。因其所具有的独特结构和性质，使其在诸多领域有广泛的应用前景。目前，嵌套结构纳米材料多基于模板辅助的方式制备，即首先通过层层包覆合成芯-壳-壳复合材料，再通过侵蚀或焙烧方式去除中间层。然而，这些方法制备过程相对复杂，可能引入有机物杂质，且不利于大规模生产。本项目拟采用单轴静电纺丝技术与氟化焙烧高效结合的新技术，直接构筑出一维嵌套结构纳米材料，包括管套线结构和带套带结构柔性纳米材料。通过调控合成参数，实现产物结构、尺寸和形貌可控，阐明其形成机理，建立一种简单、高效、普适通用的一维嵌套结构纳米的制备新技术。本项目中所要构筑的管套线结构和带套带结构柔性纳米材料是以稀土氟化物为芯、二氧化硅为壳。这种具有特殊结构的一维纳米材料将实现光磁双功能特性和柔性、亲水性及载药性的高度集成。该设计理念对特殊结构纳米材料的构筑提供理论与技术支持。

一维嵌套结构纳米材料是在其内外层间存在空隙的特殊结构纳米材料。目前，嵌套结构纳米材料多基于模板辅助的方式制备，即首先通过层层包覆合成芯-壳-壳复合材料，再通过侵蚀或焙烧方式去除中间层。然而，这些方法制备过程相对复杂，可能引入有机物杂质，且不利于大规模生产。本项目通过设计纺丝液的组成，采用单轴静电纺丝技术与氟化焙烧高效结合的新技术，直接构筑出一维嵌套结构纳米材料，包括GdF3:Eu3+@void@SiO2管套线结构纳米纤维、LnF3@void@SiO2 (Ln=Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)管套线结构纳米纤维、GdF3:10%Yb3+,0.5%Er3+@void@SiO2带套带结构纳米带、CaF2:Eu2+/3+纳米纤维、空心纳米纤维和纳米带、CaF2:9%Eu2+/3+@void@SiO2和CaFCl:7%Eu2+/3+@void@SiO2管套线结构纳米纤维和带套带结构纳米带，以及GdOF:Er3+纳米纤维。样品同时具有良好的荧光性质和顺磁性质。通过调控合成参数，实现产物结构、尺寸和形貌可控，阐明其形成机理，建立了一种简单、高效、普适通用的一维嵌套结构纳米的制备新技术。我们首次设计的制备管套线结构纳米纤维的技术具有简便、成本低、不引入有机物等优点。管套线结构纳米纤维是一种具有大长径比的材料，它的特殊的中空结构可以更方便的载药、脱Li嵌Li以及催化等，所以在生物诊疗、纳米传感器、锂离子电池及催化还原等领域有广阔的应用空间。这种具有特殊结构的一维纳米材料实现了光磁双功能特性和柔性、亲水性及载药性的高度集成。该设计理念拓展了静电纺丝的应用领域，对特殊结构纳米材料的构筑提供理论与技术支持。