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过渡金属钌配合物纳米球及铱配合物的复合纳米纤维的发光及传感性能研究
Luminescent and Oxygen Sensing Properties of the Transition Metal Ir(Ⅲ) Complex Nanofibers and Ru(Ⅱ) Complex Nanoparticles
【作者】 王术立;
【导师】 李斌;
【作者基本信息】 东北师范大学 , 无机化学, 2010, 硕士
【摘要】 纳米材料由于其优良的综合性能,特别是其性能的可设计性被广泛应用于多个领域,其中具有新性质、新功能的有机-无机复合纳米发光材料由于兼具了纳米材料和发光材料的双重优点而受到人们的关注。在发光材料中,过渡金属铱和钌的有机配合物得到了广泛的研究,因为它们在室温下具有高的发光效率、良好的热稳定性、化学稳定性和光化学稳定性等许多优点。在这里我们通过纳米技术制备了掺杂过渡金属钌和铱的有机配合物的纳米发光纤维及纳米球材料,期望为实现纳米光电器件和生物体内氧气传感提供基础数据。本文设计合成了钌配合物[Ru(Bphen)2Phen–Si]Cl2,利用共价嫁接技术将该配合物连接至二氧化硅纳米球的表面壳层,从而得到了具有良好分散性的集发光及传感性能于一体的复合纳米材料。通过调控纳米球的粒径,实现了传感性能的优化。与原纯钌配合物相比,抑制了配合物的非辐射跃迁,使得复合纳米材料的荧光衰减寿命有所增长,在氧气浓度为0-60%时,该复合纳米材料对氧浓度呈较好的线性关系。通过嫁接方法将配合物与无毒二氧化硅核壳结构相连,为测定生物体内低浓度氧的含量提供了可能。设计合成了铱的配合物Ir(ppy)2Bphen,并以聚乙烯吡咯烷酮(PVP)为前驱体溶液制得了Ir(ppy)2Bphen/PVP复合纳米发光纤维,通过荧光光谱分析、荧光寿命测试、扫描电镜等分析手段对样品进行了表征,纤维表面形貌光滑不粘连,直径在245-590nm之间,研究了配合物浓度对纤维直径和形态及发光强度的影响,发现当掺杂浓度为0.20%,复合纤维材料具有最佳的发光强度,并通过对纺丝这种载体使配合物激发态寿命延长。
【Abstract】 Nanomaterials have been widely used in many fielde due to it’s excellent performance, especially its performance can be planned. In recent years nano-composite materials is one of the most attractive part of the developed rapidly.Many developed countries regards the development of strategies for the nano-composite materials as important position. But with the new nature, features of organic-inorganic composite nano-light-emitting materials are preferred, because it combines nano-materials and the dual advantages of luminescent materials. In the light-emitting materials, transition metal iridium and ruthenium have been extensively studied, because the transition metal-organic complexes have good light-emitting efficiency, thermal stability, chemical stability and photochemical stability, and many other advantages. In this paper, we got nanospheres of [Ru(Bphen)2Phen-Si]Cl2 and Ir(ppy)2Bphen/PVP nanofibers by nanotechnology at room temperature.We designed and synthesized [Ru(Bphen)2Phen-Si]Cl2, it was linked to the surface shell-layer of SiO2 nanospheres by useing of covalently grafting, then obtained nanocomposites with good dispersion, which have good luminescence and sensing properties. Realized sensing performance optimization by regulating nanospheres’diameter. The excited states of composite materials life have been increased compare with pure complex because the non-radiative transition of complex has been inhibited. we get a good linear relationship between the composite and the concentration of oxygen by testing the oxygen concentration from 0 to 60%. The complex was linked to non-toxic SiO2 nanospheres surface shell-layer, which make them candidates for monitoring the dissolved oxygen in liquid phase, especially could be used in biological fluids.Luminescent composite nanofibers doped with Ir(ppy)2Bphen was fabricated by electrospinning technique, using poly(vinylpyrrolidone)(PVP) as precursor. The materials were characterized by fluorescence spectrophotometers,scanning fluorescence lifetimes spectrophotometer and electron microscope(SEM), nanofibers with smooth and less beads and branches were obtained, the average diameter were between 245 and 590nm. We studied the concentration of complex affect on fibers’morphology, diameter and the luminescen intensity, when doping concentration’s of complex was 0.20%, Composite materials have the best luminescence intensity, and the excited states of complex life have been increased by fibers.
【Key words】 SiO2 Nanospheres; Electrospinning; Ruthenium Ccomplex; Iridium Complex;