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纸质出版日期:2008-5-20,
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殷广明, 邓启刚, 毕野, 杨万丽, 吕仁江, 周德瑞. 模板合成H4PMo11VO40/聚苯胺纳米线列阵及其聚合机理探讨[J]. 高分子学报, 2008,(5):430-434.
YIN Guangming, DENG Qigang ., BI Ye, YANG Wanli, LÜ, Renjiang. Template Synthesis and Polymerization Mechanism of HPA/PANI Nanowire Arrays[J]. Acta Polymerica Sinica, 2008,(5):430-434.
殷广明, 邓启刚, 毕野, 杨万丽, 吕仁江, 周德瑞. 模板合成H4PMo11VO40/聚苯胺纳米线列阵及其聚合机理探讨[J]. 高分子学报, 2008,(5):430-434. DOI: 10.3724/SP.J.1105.2008.00430.
YIN Guangming, DENG Qigang ., BI Ye, YANG Wanli, LÜ, Renjiang. Template Synthesis and Polymerization Mechanism of HPA/PANI Nanowire Arrays[J]. Acta Polymerica Sinica, 2008,(5):430-434. DOI: 10.3724/SP.J.1105.2008.00430.
在氧化铝模板中制备了HPA/PANI纳米线列阵,SEM、TEM表明列阵中纳米线直径约为80 nm;XRD与FT-IR证明形成了有效掺杂;单根纳米线的导电率为16.2 S·cm-1;材料的TG-DTA表明PANI纳米线材料有三步失重过程,失去吸附水过程,多酸失去结晶水和PANI结构持续分解过程,多酸结构分解过程;在氧化聚合过程中H4PMo11VO40 即为质子酸又为氧化剂和掺杂剂;聚合反应采用自由基机理进行,掺杂反应发生在形成醌二亚胺式自由基正离子和双苯胺式自由基正离子和醌二亚胺式自由基正离子偶联聚合成链结构时.
By the synthetic method of chemical oxidative polymerization
conducting polyaniline (PANI) doped with vanadium-containing molybdicacid (HPA) had been prepared by template synthesis within porous anodic aluminum oxide (AAO).The porous anodic aluminum oxide membranes were immersed in the aniline monomer solution
and a vacuum was kept until no air bubble gave off in the AAO templates;in this case
the template channels were full of the aniline monomer
the HPA solution was dropped into aniline solution
and reaction was initiated inside the channels to form one-dimensional nanostructures PANI.The nanowires of the PANI were characterized by Fourier transform infrared spectroscopy (FT-IR)
the X-ray diffraction (XRD)
the scanning electron microscopy (SEM) and the transmission electron microscopy (TEM).The XRD and FT-IR spectra analysis provides evidence for the HPA/PANI that the PANI could be effectively doped by the HPA
and the HPA existed with molecular state in the materials
and the materials are of non-crystalline structure.The surface morphology of the HPA/PANI nanowire arrays was observed by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).The SEM and TEM information show that the PANI nanowires are about 80 nm in diameter.Furthermore
the thermal stability and the conductivity of doped PANI were also determined.The materials have three steps in the thermal analysis
losing adsorbed water process
losing crystalline water of the HPA structure and continous decomposition process of the PANI structure and HPA structure decomposition process.The conductivity of the HPA/PANI was determined to be 16.2 S·cm-1.In the polymerization process
the HPA not only acts as protonic acid
but also oxidant and dopant.The polymerization follows a radical mechanism:In the first the aniline is protonated by HPA
and then HPA further oxidates aniline cationic radicals.The aniline is induced to generate the quinoid dimine cationic radicals and bensoid cationic radicals
the formation of the PANI long chain results from coupling of two cationic radicals.The electron transfers from benzenoid ring segments to quinoid ring segments and further fabricates the model structure of tetracyclic anamorphosis of the benzenoid-type and quinoid-type in the chain structure of the PANI.The doping reaction undergoes in two steps
formation of the quinoid dimine cationic and their coupling with bensoid cationic radicals.
AAO模板H4PMo11VO40聚苯胺纳米线列阵聚合机理
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