两种不同途径的原位法制备PPV/AuNPs纳米复合材料及其荧光和光伏性能的研究
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摘要
纳米材料因为其优异的光学,电学,磁学等性能,得到了人们的广泛关注。近些年来,将纳米材料掺入到聚合物基质中,研究纳米粒子对聚合物性能的影响以及纳米材料和聚合物之间的相互作用的报道很多。一些研究发现,金纳米粒子(Au nanoparticles,AuNPs)会影响导电聚合物的物理、化学性质;而且复合物的制备方法和途径不同,AuNPs对同一种聚合物性质的影响也不一样。聚对苯撑乙烯(Poly(phenylene vinylene),PPV)是一种性能优异的导电聚合物材料,但是它的刚性结构使得其溶解性极差,几乎不溶于任何溶剂,这给其复合材料的制备和加工带来了困难。所以,PPV复合材料的制备都是先合成其前驱物(Poly(phenylene vinylene) precursor,PPVpre)的复合物,经过热转化得到PPV的复合材料。尽管如此,PPVpre对某些溶剂和其他的有机、无机物质也很敏感。非功能性杂质的引入会影响PPV激子生成和空穴传输。而且,PPVpre的链在溶液中的顺式、反式和顺向式三种构象,可能会对纳米粒子的均匀分散产生影响。因此,选择合适的方法制备PPV纳米复合材料是一个值得研究的课题。
在本文中,我们用原位合成法,在不引入其他配体保护AuNPs的条件下,通过两种不同的途径成功的制备了PPV/AuNPs纳米复合材料。原位一法是在双锍盐体系中用NaBH4还原HAuCl4先制备出AuNPs,然后滴加NaOH聚合得到PPVpre/AuNPs复合物,最后通过热转化制备出PPV/AuNPs复合材料;原位二法是在渗析后的PPVpre体系中用NaBH4还原HAuCl4制备PPVpre/AuNPs复合物,最后通过热转化制备PPV/AuNPs复合材料。
我们对两种合成途径得到的PPV/AuNPs纳米复合材料进行了结构,形貌,荧光性质和光伏特性的表征,对测试结果进行了对比,并讨论了两种不同合成途径对性能影响的因素。我们的研究为PPV在光电子器件领域的发展提供了新的参考。
Nanomaterials are received much attention due to their excellent properties in optical, electrical and magnetic properties. There are many reports about incorporating nanoparticles into polymer matrix and investigating on the interaction between them. They find that Au nanoparticles (AuNPs) can influence the chemical and physical properties of conductive polymer. Properties of the composite are also affected by preparing methods and routes. Poly(phenylene vinylene) (PPV) is an excellent conductive polymer. Its rigid structure makes it almost insoluble in any solvent, which brings difficulties to preparation and processing of PPV’s nanocomposites. So we always prepare the PPV precursor (PPVpre) composite, and then convert into PPV composite at high temperature. However, PPVpre is sensitive to many solvents and inorganic and organic substances. The cis, trans and cisoid structure of PPVpre in solution may affect the distribution of nanoparticles. Some nonfunctional materials may affect the generation of exciton and transport of hole. Therefore, choosing a suitable method or route for preparation of PPV composite is very important.
In this text, we prepared PPV/AuNPs nanocomposite by two different in-situ routes without using any ligand. Both of them obtained PPV/AuNPs nanocomposite by thermal conversion from PPVpre/AuNPs. The difference between them was the preparation of PPVpre/AuNPs. One was using NaBH4 reduce HAuCl4 in two-sulfur salt system at first, and then drop NaOH into the solution for polymerization to form PPV/AuNPs (in-situ route 1). The other was preparing AuNPs in after dialysis PPVpre (in-situ route 2).
We characterized the structure, morphology, fluorescence properties and photovoltaic property. Compared the properties of PPV/AuNPs by using two different routes and discussed the possible reasons for AuNPs impact on nature of PPV. This study provides a new guidance for development of PPV in optic-electric devices.
在本文中,我们用原位合成法,在不引入其他配体保护AuNPs的条件下,通过两种不同的途径成功的制备了PPV/AuNPs纳米复合材料。原位一法是在双锍盐体系中用NaBH4还原HAuCl4先制备出AuNPs,然后滴加NaOH聚合得到PPVpre/AuNPs复合物,最后通过热转化制备出PPV/AuNPs复合材料;原位二法是在渗析后的PPVpre体系中用NaBH4还原HAuCl4制备PPVpre/AuNPs复合物,最后通过热转化制备PPV/AuNPs复合材料。
我们对两种合成途径得到的PPV/AuNPs纳米复合材料进行了结构,形貌,荧光性质和光伏特性的表征,对测试结果进行了对比,并讨论了两种不同合成途径对性能影响的因素。我们的研究为PPV在光电子器件领域的发展提供了新的参考。
Nanomaterials are received much attention due to their excellent properties in optical, electrical and magnetic properties. There are many reports about incorporating nanoparticles into polymer matrix and investigating on the interaction between them. They find that Au nanoparticles (AuNPs) can influence the chemical and physical properties of conductive polymer. Properties of the composite are also affected by preparing methods and routes. Poly(phenylene vinylene) (PPV) is an excellent conductive polymer. Its rigid structure makes it almost insoluble in any solvent, which brings difficulties to preparation and processing of PPV’s nanocomposites. So we always prepare the PPV precursor (PPVpre) composite, and then convert into PPV composite at high temperature. However, PPVpre is sensitive to many solvents and inorganic and organic substances. The cis, trans and cisoid structure of PPVpre in solution may affect the distribution of nanoparticles. Some nonfunctional materials may affect the generation of exciton and transport of hole. Therefore, choosing a suitable method or route for preparation of PPV composite is very important.
In this text, we prepared PPV/AuNPs nanocomposite by two different in-situ routes without using any ligand. Both of them obtained PPV/AuNPs nanocomposite by thermal conversion from PPVpre/AuNPs. The difference between them was the preparation of PPVpre/AuNPs. One was using NaBH4 reduce HAuCl4 in two-sulfur salt system at first, and then drop NaOH into the solution for polymerization to form PPV/AuNPs (in-situ route 1). The other was preparing AuNPs in after dialysis PPVpre (in-situ route 2).
We characterized the structure, morphology, fluorescence properties and photovoltaic property. Compared the properties of PPV/AuNPs by using two different routes and discussed the possible reasons for AuNPs impact on nature of PPV. This study provides a new guidance for development of PPV in optic-electric devices.
引文
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[6] Cheng Wang, Eryun Yan, Zonghao Huang, Qiang Zhao et al. Fabrication of Highly Photoluminescent TiO2/PPV Hybrid Nanoparticle-Polymer Fibers by Electrospinning[J]. Macromol Rapid Commun.2007, 28: 205–209.
[7] Zijiang Jiang, Zonghao Huang, Peipei Yang, Jinfeng Chen. High PL-efficiency ZnO nanocrystallites/PPV composite nanofibers[J]. Composites Science and Technology,2008,68:3240-3244.
[8] P.P.Yang, J.F.Chen, Z.H.Huang, S.M.Zhan. A novel 1D organic optic–electronic nanomaterial using PPV(p-type)as shell and Alq3(n-type)as core[J]. Materials Letters,2009,63: 1978–1980.
[9] Yi Xin, Zonghao Huang, Peipei Yang, Zijiang Jiang. Controlling the Deposition of Light-Emitting Nanofibers/Microfibers by the Electrospinning of a Poly(p-phenylene vinylene)Polyelectrolyte Precursor[J]. Journal of Applied Polymer Science, 2009, 114: 1864-1869.
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