静电纺丝法制备微纳米过渡金属氧化物及其性能研究

发布时间：2018-04-01 13:22

本文选题：静电纺丝　切入点：过渡金属氧化物　出处：《吉林大学》2015年博士论文

【摘要】：近年来，纳米级过渡金属氧化物因具有良好的电、光、力学等性能逐渐成为研究热点。静电纺丝法凭借其操作简单、方便等优势，成为制备纳米金属氧化物纤维的主要手段。然而，传统静电纺丝法制备纳米金属氧化物材料还存在形貌过于单一、应用性不强等局限性。基于这种现状，完善纳米纤维材料的制备方法是必要的。由此，本论文提出了静电纺丝法分别结合溶胶-凝胶、物质改性、物理吸附、液-固反应等技术，以得到形貌多样、应用性强的产物。金属氧化物纤维的形貌和性质还受静电纺丝过程中聚合物参数的影响。为了探究聚合物模板对氧化物纤维形貌的影响行为，本论文选取三种合成高分子材料作为模板，制备了几种形貌特殊的纳米过渡金属氧化物，并对其形成机理进行了研究。主要工作内容如下：第一，以聚乳酸（PLA）为模板，利用静电纺丝法分别结合溶胶-凝胶、物质改性、物理吸附的技术制备出表面带有条纹的TiO2纳米纤维、ZnO纳米纤维及具有多层结构的纳米NiO产物，既简化了过渡金属氧化物纳米纤维的制备过程，又解决了ZnO纤维无法通过直接煅烧制备的问题。通过对上述纤维的光催化活性、气体传感性的研究，发现新形貌有利于提高性能。第二，利用一步扩链法合成(ABA)n型聚乳酸-聚己内酯二元醇共聚物（PCLA），并以其为模板，通过静电纺丝法结合溶胶-凝胶及煅烧技术制备出形貌特殊的Mn2O3纳米褶皱和Mn3O4纳米棒，并研究其催化性质。此外，还将PCLA作为底物，通过溶剂-紫外光结合法原位还原Ag+制备出负载Ag纳米颗粒（AgNPs）的PCLA纤维。该方法解决了普通溶剂还原法耗时长、粒子易团聚的问题，实现了纳米粒子在聚合物纤维中的均匀分散。第三，以含苯羧基线性聚芳醚酮（PCA-PAEK）为中心，首次制备出纯PCA-PAEK超细纤维，，并以其为模板，利用液-固反应结合煅烧技术，分别制备出绳索状的CuO纤维、带孔的CdO纤维及镂空的CuO/CdO复合纤维，实现了不同成分金属氧化物纳米纤维的制备。通过对上述金属氧化物形貌形成机制的研究，发现金属氧化物的最终形态与聚合物模板的选择有密切联系。
[Abstract]:In recent years, nanoscale transition metal oxides have become a hot research area due to their excellent electrical, optical and mechanical properties.Electrostatic spinning has become the main method to prepare nano-metal oxide fiber because of its advantages such as simple operation and convenience.However, the traditional electrospinning method still has some limitations such as too single morphology and weak application.Based on this situation, it is necessary to perfect the preparation method of nanofiber materials.Therefore, the electrospinning method combined with sol-gel, material modification, physical adsorption, liquid-solid reaction and so on was proposed in this paper to obtain the products with various morphology and strong application.The morphology and properties of metal oxide fibers are also affected by polymer parameters during electrostatic spinning.In order to investigate the effect of polymer template on the morphology of oxide fibers, three kinds of synthetic polymer materials were selected as templates to prepare several nano-transition metal oxides with special morphology, and their formation mechanism was studied.The main tasks are as follows:Firstly, TiO2 nanofibers with striped surface and nanosized NiO products with multilayer structure were prepared by electrospinning with sol-gel modification and physical adsorption using polylactic acid (PLA) as template.It not only simplifies the preparation process of transition metal oxide nanofibers, but also solves the problem that ZnO fibers can not be prepared by direct calcination.Through the study of the photocatalytic activity and gas conductivity of the fibers, it is found that the new morphology is beneficial to the improvement of the performance.Secondly, Mn2O3 nanorods and Mn3O4 nanorods with special morphology were synthesized by one-step chain extension method, and the Mn2O3 nanorods with special morphology were prepared by electrospinning method combined with sol-gel and calcination techniques, using the poly (lactic acid-polycaprolactone) diol diol copolymers as a template.Its catalytic properties were studied.In addition, PCLA was used as substrate to prepare PCLA fibers loaded with Ag nanoparticles by in situ reduction of Ag by solvent-UV combination method.This method solves the problem of long time consuming and easy agglomeration of particles in ordinary solvent reduction method, and realizes the uniform dispersion of nanoparticles in polymer fibers.Thirdly, the pure PCA-PAEK ultrafine fiber was prepared by using linear polyaryl ether ketone (PCA-PAEK) containing benzene carboxyl group as the center for the first time. Using it as a template, the cord-like CuO fibers were prepared by liquid-solid reaction combined with calcination technology, respectively.The preparation of metal oxide nanofibers with different composition was realized by porous CdO fiber and hollow CuO/CdO composite fiber.It is found that the final morphology of metal oxides is closely related to the selection of polymer templates.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.1;TQ340.64

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