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镍对铁磁性导电聚苯胺性能的影响
【作者】 张娅；
【导师】 阚锦晴；
【作者基本信息】 扬州大学 ， 物理化学， 2008， 硕士
【摘要】 一、导电铁磁性聚苯胺的合成及反应时间对其性质的影响室温和不同反应时间条件下,在含有适量六水合氯化镍的苯胺(0.1 mol dm-3)与盐酸(0.5 mol dm-3)混合液中合成得到铁磁性导电聚苯胺,使用过硫酸铵为氧化剂。所得产物的电导率在10-1~10-2 S cm-1数量级。产物的电子顺磁共振波谱表明:反应8小时得到的聚苯胺具有最窄的线宽值(△H pp=1.96)和最大的电子自旋密度值(2.36×1020 spins g-1)。磁化率与磁场强度曲线表明:产物聚苯胺在300K时具有软铁磁行为,其中合成8小时得到的聚苯胺具有最大的饱和磁化率(0.050 emu g-1)。紫外光谱和红外光谱表明在镍离子与聚苯胺链之间存在相互作用,且在磁场条件下加入六水合氯化镍合成得到的聚苯胺的骨架结构与不加六水合氯化镍合成得到的聚苯胺的骨架结构几乎相同。循环伏安结果表明:在含有六水合氯化镍条件下合成的聚苯胺具有电化学活性。二、室温下酶法合成铁磁性导电聚苯胺铁磁性聚苯胺在分别在含和不含六水合氯化镍的苯胺与盐酸体系中被合成,使用辣根过氧化酶作催化剂,过硫酸铵为氧化剂。所得产物的电导率在10-1 S cm-1数量级。产物的电子顺磁共振波谱表明:合成时加入六水合氯化镍的聚苯胺中含有成单电子,计算得到电子自旋密度为1.09×1019 spins g-1,该值明显高于合成时不加六水合氯化镍的聚苯胺(其电子自旋密度为1018 spins g-1)。磁化率与磁场强度曲线表明:合成时加入六水合氯化镍的聚苯胺在300K时具有软铁磁行为,它的饱和磁化率为0.018 emu g-1,矫顽力约为55 Oe。产物的紫外光谱和红外光谱表明:镍离子与聚苯胺链之间存在相互作用,且加入六水合氯化镍合成得到的聚苯胺的骨架结构与不加六水合氯化镍合成得到的聚苯胺的骨架结构几乎相同。三、外加磁场条件下酶法合成铁磁性导电聚苯胺在外加磁场中,铁磁性导电聚苯胺在含有六水合氯化镍的苯胺与盐酸的4-羟乙基哌嗪乙磺酸缓冲体系中被合成,使用辣根过氧化酶作催化剂,过硫酸铵为氧化剂。产物的电子顺磁共振波谱表明:合成时加入六水合氯化镍的聚苯胺中含有成单电子,计算得电子自旋密度为7.60×1019 spins g-1。磁化率与磁场强度曲线表明:合成时加入六水合氯化镍的聚苯胺在300 K时具有软铁磁行为,它的饱和磁化率和矫顽力分别为0.033 emu g-1和5 Oe。紫外光谱和红外光谱表明在镍离子与聚苯胺链之间存在相互作用,且在磁场条件下加入六水合氯化镍合成得到的聚苯胺的骨架结构与不加六水合氯化镍合成得到的聚苯胺的骨架结构几乎相同。
【Abstract】 1. Study on Synthesis and Characterization of Ferromagnetic Conducting PolyanilineFerromagnetic polyaniline were synthesized in a solution containing 0.1 mol dm-3 aniline, 0.5 mol dm-3 HCl and adequate NiCl2·6H2O at ambient temperature, using peroxydisulphate as an oxidant. The conductivities of the resulting products were in the magnitude order of 10-1~10-2 S cm-1. The results of electron paramagnetic resonance (EPR) spectra indicated that the PANI synthesized with NiCl2·6H2O for 8 hours had the narrowest line width (△H pp=1.96) and the maximum spin density (2.36×1020 spins g-1). The magnetization (M)–magnetic field (H) curves showed that the polyaniline was ferromagnetic behavior at room temperature. The PANI synthesized with NiCl2·6H2O for 8 hours had the largest saturation magnetization (Ms) of 0.050 emu/g. UV-vis and FTIR spectra showed that there was strong interaction between Ni2+ and PANI chains but the backbone chains of PANI were hardly changed compared with PANI synthesized without NiCl2·6H2O. Cyclic voltammogram results indicated that the PANI film synthesized with NiCl2·6H2O was of excellent electrochemical activity.2. Both Conducting and Ferromagnetic Polyaniline at Ambient TemperatureFerromagnetic polyaniline were synthesized in aniline and HCl with and without NiCl2·6H2O, using peroxydisulphate as an oxidant and horseradish peroxidase as a catalyst. The conductivity of the resulting product was about 10-1 S cm-1. The result of electron paramagnetic resonance (EPR) spectra indicated that there were unpaired electrons in PANI synthesized with NiCl2·6H2O and the spin density of the PANI was 1.09×1019 spins g-1, which was more than the PANI (1018 spins g-1) synthesized without NiCl2·6H2O. The magnetization (M)–magnetic field (H) curve showed that PANI synthesized with NiCl2·6H2O was of soft ferromagnetic behavior at about 300 K and its saturation magnetization (Ms) was 0.018 emu g-1 (electromagnetic unit per gram) and the coercive force (Hc) was about 55 Oe. UV-vis and FTIR spectra showed that there was strong interaction between Ni2+ and PANI chains but the backbone chains of PANI were hardly changed compared with PANI synthesized without NiCl2·6H2O.3. Synthesis and Characterization of Ferromagnetic Polyaniline with Conductivity in Applied Magnetic FieldFerromagnetic polyaniline (PANI) with conductivity were synthesized using peroxydisulphate as an oxidant and horseradish peroxidase as a catalyst in N’-a-hydroxythylpiperazine-N’-ethanesulfanic acid (HEPES) buffer solution containing aniline, HCl and NiCl2·6H2O in applied magnetic field. The result of EPR spectrum indicated that there were unpaired electrons in the resulting product, the spin density of which was 7.60×1019 spins g-1. The curve of magnetization (M)–magnetic field (H) showed that the PANI was of soft ferromagnetic behavior at about 300 K. The saturation magnetization (Ms) and the coercive force (Hc) of the PANI were 0.033 emu g-1 (electromagnetic unit per gram) and 5 Oe, respectively. UV-vis and FTIR spectra indicated that there was interaction between Ni2+ and PANI chains but the structure of backbone chains of PANI synthesized in the presence of magnetic field hardly changed when compared with PANI synthesized without NiCl2·6H2O.