聚苯胺與金屬奈米結構複合材料之研究

洪筱鵬(Shiau-Peng Hung)

指導教授 ： 楊思明

國立中央大學/工學院/化學工程與材料工程學系/碩士(2006年)

摘要

摘要
本研究主題主要有兩大部分:第一部分利用過硫酸銨或四氯金酸做為氧化劑,在氧化鋁濾膜或聚碳酸酯膜的模板中,化學合成聚苯胺奈米管。並藉由SEM及TEM影像觀察聚苯胺奈米管的表面形態及中空管柱結構。以FT-IR鑑定在模板中化學合成的產物是否為聚苯胺結構。另一方面,亦利用四氯金酸/硝酸銀/硫酸銅/硝酸鈀做為氧化劑,直接與苯胺鹽單體進行化學合成。藉由SEM影像分析聚苯胺纖維的表面形態；以及金屬顆粒沉積的現象。再者,以TEM影像分析聚苯胺及金屬複合材料,由EDX分析金屬顆粒成份；再由選區電子繞射(SAED)來判別聚苯胺及金屬複合材料中金屬顆粒的晶型,並且可知道其晶格構造。由FT-IR鑑定這些不同氧化劑與苯胺鹽單體間所形成的產物是否為聚苯胺結構。最後以四點探針去量測聚苯胺及金屬複合材料塊材的導電度。
第二部分則利用聚苯胺具有還原的特性，以聚苯胺奈米管將金、銀、銅或鈀離子還原,因此可得到聚苯胺金/銀/銅/鈀雙層奈米管。本研究以氧化鋁膜或聚碳酸酯膜做為模板,利用電化學法先合成聚苯胺的管狀結構，再將聚苯胺管浸置於HAuCl4/AgNO3/CuSO4/Pd(NO3)2溶液中，即可得到聚苯胺金/銀/銅/鈀雙層管，並利用NMP將聚苯胺完全溶解後,即可得到金、銀、銅或鈀奈米管。另一方面,本研究也利用無電電鍍的方法,成功製備出聚苯胺銅/鎳奈米雙層管。先將電化學合成的聚苯胺管浸置於無電電鍍銅或無電電鍍鎳的混合溶液中，利用還原劑將銅或鎳離子還原並沉積在聚苯胺管,如此可製備出聚苯胺銅或鎳的奈米雙層管。藉由SEM影像觀察聚苯胺金屬雙層管及奈米金屬管的表面型態；並利用EDX成份分析確定是否為金、銀、鈀、銅或鎳管。以TEM影像分析所合成的聚苯胺金屬雙層管的內部結構；另外,由選區電子繞射(SAED)、暗視野影像(DF)分析各種不同金屬管的晶型及晶格結構；並以EDX成份分析確定是否為金、銀、鈀、銅或鎳管。由FT-IR鑑定在不同模板及孔徑中,其電化學合成的產物是否為聚苯胺結構。最後以循環伏安圖譜(CV)分析在不同模板及孔徑中,聚苯胺管的不同氧化態。

關鍵字

暗視野影像 ； 循環伏安圖譜 ； 雙層奈米管 ； 選區電子繞射

並列摘要

Abstract
In this study, we have two main topics: Firstly, we synthesized polyaniline (PANI) nanotubes using ammonium peroxydisulfate (APS) or chloroaurate acid (HAuCl4) as the oxidant by chemical method within the pores of anodic aluminum membrane (AAO) or polycarbonate track-etched membrane (PTM). We observe the surface morphology and hollow tube structure of PANI nanotubes by SEM and TEM photographs. From the study of FT-IR spectra, we confirm that the product is PANI produced in the pores of the template. On the other hand, we also use aqueous solutions of HAuCl4/ AgNO3/CuSO4/Pd(NO3)2 as the oxidant for the synthesis of PANI/metal composites. We observe the composites of PANI fibers and metal particles by SEM and TEM photographs. In addition, the metal particles formation can be proved from EDX analysis. Selected area electron diffraction (SAED) results indicate the crystal type and structure of the metal particles in PANI/metal composites material. We confirm that the product is PANI produced from the reaction between aniline and HAuCl4/ AgNO3/CuSO4/Pd(NO3)2 by means of FT-IR spectra. we also measure the conductivity of PANI/metal composites bulk material by Four-Point Conductive measurements.
Secondly, we can prepare gold/silver/copper/palladium nanotubes by reducing ability of PANI nanotubes. In this study, we use AAO or PTM as templates to synthesize PANI nanotubes by electrochemical method. AAO or PTM with PANI nanotubes were then immersed in HAuCl4 /AgNO3/CuSO4/Pd(NO3)2 solution. PANI Au/Ag/Cu/Pd bilayer nanotubes can be obtained. After dissolving polyaniline with NMP, then we obtain Au/Ag/Cu/Pd nanotubes. Besides, we also prepare PANI Cu/Ni bilayer nanotubes by electroless plating method. AAO or PTM with PANI nanotubes were immersed in electroless plating of copper or nickle solution.Therefore,we can obtain PANI Cu/Ni bilayer nanotubes by reductant to reduce copper or nickle ions and deposit them in PANI nanotubes. Cu/Ni nanotubes can be obtained by dissolving PANI with NMP. We observe the surface morphology of PANI metal bilayer nanotubes or metal nanotubes by SEM photographs. In addition, the formation of Au/Ag/Cu/Pd/Ni nanotubes can be proved from EDX analysis. We also observe hollow tube structure of PANI metal bilayer nanotubes from TEM photographs. Furthermore, SAED and Dark Field (DF) results indicate the crystal type and structure of the metal tube. The reduction/oxidation (redox) behaviors of PANI nanotubes within AAO or PTM in HCl solution were studied by Cycilic Voltammmetry.

並列關鍵字

Dark Field ； Selected area electron diffraction ； bilayer nanotubes ； Cycilic Voltammmetry

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