杂多酸/聚吡咯功能复合材料的合成、表征及性质研究
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摘要
有机—无机复合物作为一类新颖的复合材料,既有金属和无机半导体的电学、光学和磁学特性,又有有机聚合物柔韧的机械性能和可加工性能,同时还有电化学氧化还原性,因此成为科学研究的焦点。它们在电池的电极材料、电催化、光学显示器件、传感器、电磁屏蔽、非线性光学器件、微电子和金属防腐等技术领域都有广泛的应用前景。本论文采用电化学聚合法、化学氧化法和固相反应法制备了杂多酸-聚吡咯功能复合材料。主要研究结果如下:
1.电化学法制备PPy/SiW11Ni磁性复合膜。在含有杂多酸和吡咯单体的电解液中采用恒电流方法制备了PPy/SiW11Ni磁性复合膜,该方法的优点是膜的形成和掺杂同时进行,并且便于现代检测技术的运用。Raman、电化学和磁性结果表明,杂多酸已经掺杂于聚合物中。TG测试考察了复合物的热稳定性。同时,我们详细考察了膜厚对电化学性质的影响。
2.化学氧化法制备PPy/CoW12复合材料。在不引入其他掺杂离子的情况下,首次运用磁性杂多酸作为单体吡咯的氧化剂,合成了具有导电性和磁性的双功能复合材料。同时,运用红外、TG-DTA、EDX、电化学、磁性和导电性等手段对复合物进行表征和研究。
3.固相反应法制备PPy/CoW12复合材料。固相反应法不使用溶剂(绿色环保),具有高选择性、高产率、低能耗、工艺过程简单等优点而备受重视。我们首次运用固相反应法制备了PPy/CoW12复合材料,并对材料进行了电化学性质研究。探讨了扫描速度、电解质浓度以及亚硝酸根浓度对复合物电化学行为的影响。
Organic-inorganic hybrids as a new composite material have attracted great attention in technological and scientific fields, because they have electrical, optical and magnetic properties of metal and inorganic semiconductor, and flexile mechanical performance and processibility of organic polymer, as well as electrochemical redox activity. These hybrid materials have potential applications in practice, such as rechargeable batteries, electrocatalysis, optical displays, sensors, electromagnetic radiation shielding, nonlinear optics, microelectronics, and corrosion protection. In this paper, we report the synthesis and characterization of PPy/POM composites by electro polymerization, chemical oxidation and solid phase polymerization methods. The main results are summarized as follows:
1. PPy/SiW11Ni hybrid films have been prepared by electro polymerization. The magnetic hybrid films (PPy/SiW11Ni) have been prepared by galvanostatic at 1.00 mA from aqueous solutions containing pyrrole and POM anion in three-electrode cell. An advantage of this method was formation of the films and the doping occurred simultaneously. And this method is favorable to examine the characterization of the hybrid materials using modern technologies. Raman, electrochemical and magnetic properties indicated the presence of the POM in the hybrids. To determine the thermal stability of the sample, we carried out TG measurement of the hybrid film. And we studied the influence of the film thickness on the electrochemical property in detail.
2. PPy/CoW12 hybrid material has been prepared by chemical oxidation. We report the first example of hybrid material combining organic polymer and magnetic POM by chemical oxidation, wherein 12-Tungstocobaltiate [CoⅢW12O40]5- (CoⅢW12) and polypyrrole (PPy) are used as the inorganic oxidant and the conducting matrix, respectively, without other inactive anions. The details of the synthesis are given, with a full characterization by FTIR spectroscopy, thermal analyses, EDX, electrochemistry, conductivity and magnetic susceptibility.
3. PPy/CoW12 hybrid materials have been prepared by solid phase polymerization. Solid-state synthesis method, which is friendly to environment, has been paid great attention due to its high selectivity, high productivity, low cost and no solvent, as well as the process of facture is simple and easy. CoW12-based organic-inorganic hybrid material PPy/CoW12 has been prepared by solid phase polymerization for the first time. The electrochemical behavior of the chemical modified electrode has been studied in detail, including scan rate, the concentration of the electrolyte and the concentration of the NO2- anion.
1.电化学法制备PPy/SiW11Ni磁性复合膜。在含有杂多酸和吡咯单体的电解液中采用恒电流方法制备了PPy/SiW11Ni磁性复合膜,该方法的优点是膜的形成和掺杂同时进行,并且便于现代检测技术的运用。Raman、电化学和磁性结果表明,杂多酸已经掺杂于聚合物中。TG测试考察了复合物的热稳定性。同时,我们详细考察了膜厚对电化学性质的影响。
2.化学氧化法制备PPy/CoW12复合材料。在不引入其他掺杂离子的情况下,首次运用磁性杂多酸作为单体吡咯的氧化剂,合成了具有导电性和磁性的双功能复合材料。同时,运用红外、TG-DTA、EDX、电化学、磁性和导电性等手段对复合物进行表征和研究。
3.固相反应法制备PPy/CoW12复合材料。固相反应法不使用溶剂(绿色环保),具有高选择性、高产率、低能耗、工艺过程简单等优点而备受重视。我们首次运用固相反应法制备了PPy/CoW12复合材料,并对材料进行了电化学性质研究。探讨了扫描速度、电解质浓度以及亚硝酸根浓度对复合物电化学行为的影响。
Organic-inorganic hybrids as a new composite material have attracted great attention in technological and scientific fields, because they have electrical, optical and magnetic properties of metal and inorganic semiconductor, and flexile mechanical performance and processibility of organic polymer, as well as electrochemical redox activity. These hybrid materials have potential applications in practice, such as rechargeable batteries, electrocatalysis, optical displays, sensors, electromagnetic radiation shielding, nonlinear optics, microelectronics, and corrosion protection. In this paper, we report the synthesis and characterization of PPy/POM composites by electro polymerization, chemical oxidation and solid phase polymerization methods. The main results are summarized as follows:
1. PPy/SiW11Ni hybrid films have been prepared by electro polymerization. The magnetic hybrid films (PPy/SiW11Ni) have been prepared by galvanostatic at 1.00 mA from aqueous solutions containing pyrrole and POM anion in three-electrode cell. An advantage of this method was formation of the films and the doping occurred simultaneously. And this method is favorable to examine the characterization of the hybrid materials using modern technologies. Raman, electrochemical and magnetic properties indicated the presence of the POM in the hybrids. To determine the thermal stability of the sample, we carried out TG measurement of the hybrid film. And we studied the influence of the film thickness on the electrochemical property in detail.
2. PPy/CoW12 hybrid material has been prepared by chemical oxidation. We report the first example of hybrid material combining organic polymer and magnetic POM by chemical oxidation, wherein 12-Tungstocobaltiate [CoⅢW12O40]5- (CoⅢW12) and polypyrrole (PPy) are used as the inorganic oxidant and the conducting matrix, respectively, without other inactive anions. The details of the synthesis are given, with a full characterization by FTIR spectroscopy, thermal analyses, EDX, electrochemistry, conductivity and magnetic susceptibility.
3. PPy/CoW12 hybrid materials have been prepared by solid phase polymerization. Solid-state synthesis method, which is friendly to environment, has been paid great attention due to its high selectivity, high productivity, low cost and no solvent, as well as the process of facture is simple and easy. CoW12-based organic-inorganic hybrid material PPy/CoW12 has been prepared by solid phase polymerization for the first time. The electrochemical behavior of the chemical modified electrode has been studied in detail, including scan rate, the concentration of the electrolyte and the concentration of the NO2- anion.
引文
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