磁性Fe_3O_4纳米粒子的液相制备新方法
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摘要
磁性纳米粒子是零维纳米材料,由于纳米尺度带来的表面效应、量子尺寸效应等使其内禀性质和外禀性质变得模糊,表现出与体相磁性材料不同的磁特性,如超顺磁性、低居里温度和高矫顽力等。Fe_3O_4纳米粒子作为一种具有反尖晶石结构的典型磁性纳米粒子,已经开始广泛应用到工业、军事、生物和医药等诸多领域。其制备方法的研究较多,但是简单实用同时便于后处理应用的却并不多见。
本论文提出了一种制备Fe_3O_4纳米粒子的新方法——区域限制部分还原沉淀路线。首先,使用微电极电化学方法监测FeCl3-Na2SO3体系中Fe(III)被部分还原为Fe(II)的反应进程,获得满足发生化学共沉淀反应的化学计量关系时,体系的FeCl3与Na2SO3两种试剂的初始物质的量的比为3 : 1,同时获知在选定体系中约10分钟后能达到这个条件。该条件实验的意义在于,通过精确的控制反应试剂的比例,使合成反应始终按照预设的方式进行,保证了制备产物的纯度及晶型。其次,选择含有复配大分子表面活性剂的乳液作为反应体系,通过乳液稳定性的显微观察,确定了当水相、油相和表面活性剂质量比35 : 4 : 1时,乳液的稳定性较好。这个条件实验为反应在受限的体系中进行提供了基础。再次,使用测定电导率的方法,确定了在选定体系中能控制的Fe(III)离子浓度最大范围在0.15 mol·L-1左右。这个条件实验确保粒子的合成在区域限制效应发挥作用的情况下进行,保证了制备粒子的粒径分布。最后,按照三个条件实验获得的条件参数成功制备出了Fe_3O_4纳米粒子,并通过改变实验参数的方法,验证了条件实验参数的正确性,同时发现了在区域限制效应起作用的范围,能够实现粒径可控制备。整个研究内容涉及到了对电化学、配位化学和胶体与界面化学等理论知识的应用。
区域限制部分还原沉淀路线制备的Fe_3O_4纳米粒子几乎是单分散的,这是由于在乳液体系中的大分子表面活性剂限制了核生成与核成长过程。此外,合成过程无需惰性氛围的保护,这是因为部分还原获得的Fe(II)是以配合物的形式存在,避免了氧化的发生。使用透射电镜、X-ray粉末衍射议、动态光散射粒径分析仪和振动样品磁强计对制备的磁性纳米粒子进行了表征。结果表明产物基本是纯的Fe_3O_4,形貌多为球形,具有完整的反尖晶石结构,粒子的尺寸较小,粒径分布较窄。纳米粒子的磁性能优异,在室温下粒径在15 nm左右的Fe_3O_4纳米粒子饱和磁化强度超过61.3 emu·g-1,表现出超顺磁性。
区域限制部分还原沉淀路线可以认为是一种具备化学共沉淀法和微乳法优点的制备磁性纳米粒子的新方法。使用这种方法在普通实验室条件下就能合成高质量的Fe_3O_4纳米粒子。因此,该法具有广阔的应用空间,能够满足很多方面的应用要求,特别是在生物学和医药学领域更具有应用前景。
Magnetic nanoparticles, also called zero-dimensional magnetic nanomaterials, have unique magnetic properties, such as superparamagnetism, low Cure Point, high coercivity and etc. Such size-depended properties are quite different from the bulk magnetic materials. The surface effects and quantum effects of nanoscaled materials bring such fantastic behaviors to magnetic nanoparticles. Fe_3O_4 is a typical ferrimagnetic material with inverted spinel crystalline structure, and its ultrafine powder had been widely applied because of industrial and military purposes. Nowadays, Fe_3O_4 nanoparticles are exploring new applications in biology and medicine. The high quality magnetic nanoparticles are the foundation of such potential researches. Therefore, a lot of preparation methods had been investigated. Actually, few of them are practical in the common lab conditions. It is without saying to apply conveniently after post processing.
This thesis reports a new approach to Fe_3O_4 nanoparticles: Partially reduced and confined precipitation route. Firstly, microelectrode electrochemical method was used to monitor the partial reduction process of ferric ion to ferrous ion in FeCl3-Na2SO3 system. The stoichiometric ratio of coprecipitation reaction was achieved when the beginning molar ratio of FeCl3 and Na2SO3 was 3:1. The system needed about 10 minutes to finish such partial reduction. The rigid control of the reagent ratio ensured the synthesis of Fe_3O_4 and avoided the occurrence of side reactions. The purity and crystalline structure of Fe_3O_4 nanoparticles were guaranteed. Secondly, an O/W emulsion was chosen as the medium of the whole reaction. The stability and dispersity of oil phase in such macromolecular surfactant emulsion had been examined by the means of fluorescent microscopic observation. The optimal constitutes of emulsion was found: the mass ratio of aqueous phase, cyclohexane (oil phase) and emulsifier was 35:4:1. Thirdly, the electrical conductivity of reagent emulsions was measured to look for the maximum concentration range of ferric ion. The confinement effect could work when the concentration was controlled around 0.15 mol·L-1. This experiment insured the narrow size distribution of synthesized nanoparticles. Finally, Fe_3O_4 nanoparticles were synthesized according to the above-mentioned three experiment findings. The validity of technological parameters was verified. The size-controlled synthesis could be achieved by altering the reagent concentration at the presence of the confinement effect. The research work related to the knowledge of electrochemistry, coordination chemistry, colloid chemistry and etc.
The synthesized Fe_3O_4 nanoparticles were almost monodispersed because the macromolecular surfactants in the emulsion confined the nucleation and the nucleus growth. Compared with microemulsion method, the much higher concentration of reactants increased the Fe_3O_4 nanoparticle yield. The intermediate of partial reduction reaction was complex which avoided the oxidation of ferrous ion, and this made the inert atmosphere unnecessary. The transmission electron microscope, X-ray powder diffractometer, dynamic light scattering particle size analyzer and vibrating sample magnetometer were used to characterize the nanoparticles. The results showed the synthesized nanoparticles were nearly pure Fe_3O_4 with inverted spinel crystalline structure, and the size distribution was narrow. The Fe_3O_4 nanoparticles with average diameter 15 nm were superparamagnetism, and the saturation magnetization exceeded 61.3 emu·g-1 at room temperature.
The partially reduced and confined precipitation route is derived from the traditional coprecipitation. It integrates the advantages of chemical coprecipitation and microemulsion method, and dispelled the drawbacks of them. Such method makes it possible to synthesize high quality Fe_3O_4 nanoparticles in the common lab conditions.
本论文提出了一种制备Fe_3O_4纳米粒子的新方法——区域限制部分还原沉淀路线。首先,使用微电极电化学方法监测FeCl3-Na2SO3体系中Fe(III)被部分还原为Fe(II)的反应进程,获得满足发生化学共沉淀反应的化学计量关系时,体系的FeCl3与Na2SO3两种试剂的初始物质的量的比为3 : 1,同时获知在选定体系中约10分钟后能达到这个条件。该条件实验的意义在于,通过精确的控制反应试剂的比例,使合成反应始终按照预设的方式进行,保证了制备产物的纯度及晶型。其次,选择含有复配大分子表面活性剂的乳液作为反应体系,通过乳液稳定性的显微观察,确定了当水相、油相和表面活性剂质量比35 : 4 : 1时,乳液的稳定性较好。这个条件实验为反应在受限的体系中进行提供了基础。再次,使用测定电导率的方法,确定了在选定体系中能控制的Fe(III)离子浓度最大范围在0.15 mol·L-1左右。这个条件实验确保粒子的合成在区域限制效应发挥作用的情况下进行,保证了制备粒子的粒径分布。最后,按照三个条件实验获得的条件参数成功制备出了Fe_3O_4纳米粒子,并通过改变实验参数的方法,验证了条件实验参数的正确性,同时发现了在区域限制效应起作用的范围,能够实现粒径可控制备。整个研究内容涉及到了对电化学、配位化学和胶体与界面化学等理论知识的应用。
区域限制部分还原沉淀路线制备的Fe_3O_4纳米粒子几乎是单分散的,这是由于在乳液体系中的大分子表面活性剂限制了核生成与核成长过程。此外,合成过程无需惰性氛围的保护,这是因为部分还原获得的Fe(II)是以配合物的形式存在,避免了氧化的发生。使用透射电镜、X-ray粉末衍射议、动态光散射粒径分析仪和振动样品磁强计对制备的磁性纳米粒子进行了表征。结果表明产物基本是纯的Fe_3O_4,形貌多为球形,具有完整的反尖晶石结构,粒子的尺寸较小,粒径分布较窄。纳米粒子的磁性能优异,在室温下粒径在15 nm左右的Fe_3O_4纳米粒子饱和磁化强度超过61.3 emu·g-1,表现出超顺磁性。
区域限制部分还原沉淀路线可以认为是一种具备化学共沉淀法和微乳法优点的制备磁性纳米粒子的新方法。使用这种方法在普通实验室条件下就能合成高质量的Fe_3O_4纳米粒子。因此,该法具有广阔的应用空间,能够满足很多方面的应用要求,特别是在生物学和医药学领域更具有应用前景。
Magnetic nanoparticles, also called zero-dimensional magnetic nanomaterials, have unique magnetic properties, such as superparamagnetism, low Cure Point, high coercivity and etc. Such size-depended properties are quite different from the bulk magnetic materials. The surface effects and quantum effects of nanoscaled materials bring such fantastic behaviors to magnetic nanoparticles. Fe_3O_4 is a typical ferrimagnetic material with inverted spinel crystalline structure, and its ultrafine powder had been widely applied because of industrial and military purposes. Nowadays, Fe_3O_4 nanoparticles are exploring new applications in biology and medicine. The high quality magnetic nanoparticles are the foundation of such potential researches. Therefore, a lot of preparation methods had been investigated. Actually, few of them are practical in the common lab conditions. It is without saying to apply conveniently after post processing.
This thesis reports a new approach to Fe_3O_4 nanoparticles: Partially reduced and confined precipitation route. Firstly, microelectrode electrochemical method was used to monitor the partial reduction process of ferric ion to ferrous ion in FeCl3-Na2SO3 system. The stoichiometric ratio of coprecipitation reaction was achieved when the beginning molar ratio of FeCl3 and Na2SO3 was 3:1. The system needed about 10 minutes to finish such partial reduction. The rigid control of the reagent ratio ensured the synthesis of Fe_3O_4 and avoided the occurrence of side reactions. The purity and crystalline structure of Fe_3O_4 nanoparticles were guaranteed. Secondly, an O/W emulsion was chosen as the medium of the whole reaction. The stability and dispersity of oil phase in such macromolecular surfactant emulsion had been examined by the means of fluorescent microscopic observation. The optimal constitutes of emulsion was found: the mass ratio of aqueous phase, cyclohexane (oil phase) and emulsifier was 35:4:1. Thirdly, the electrical conductivity of reagent emulsions was measured to look for the maximum concentration range of ferric ion. The confinement effect could work when the concentration was controlled around 0.15 mol·L-1. This experiment insured the narrow size distribution of synthesized nanoparticles. Finally, Fe_3O_4 nanoparticles were synthesized according to the above-mentioned three experiment findings. The validity of technological parameters was verified. The size-controlled synthesis could be achieved by altering the reagent concentration at the presence of the confinement effect. The research work related to the knowledge of electrochemistry, coordination chemistry, colloid chemistry and etc.
The synthesized Fe_3O_4 nanoparticles were almost monodispersed because the macromolecular surfactants in the emulsion confined the nucleation and the nucleus growth. Compared with microemulsion method, the much higher concentration of reactants increased the Fe_3O_4 nanoparticle yield. The intermediate of partial reduction reaction was complex which avoided the oxidation of ferrous ion, and this made the inert atmosphere unnecessary. The transmission electron microscope, X-ray powder diffractometer, dynamic light scattering particle size analyzer and vibrating sample magnetometer were used to characterize the nanoparticles. The results showed the synthesized nanoparticles were nearly pure Fe_3O_4 with inverted spinel crystalline structure, and the size distribution was narrow. The Fe_3O_4 nanoparticles with average diameter 15 nm were superparamagnetism, and the saturation magnetization exceeded 61.3 emu·g-1 at room temperature.
The partially reduced and confined precipitation route is derived from the traditional coprecipitation. It integrates the advantages of chemical coprecipitation and microemulsion method, and dispelled the drawbacks of them. Such method makes it possible to synthesize high quality Fe_3O_4 nanoparticles in the common lab conditions.
引文
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