CN100355661C - Method for preparing polar solvent soluble nano ferriferrous oxide granule - Google Patents
Method for preparing polar solvent soluble nano ferriferrous oxide granule Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002798 polar solvent Substances 0.000 title claims abstract description 12
- 239000008187 granular material Substances 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 70
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 150000002505 iron Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 10
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002122 magnetic nanoparticle Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen Sodium oxide Chemical class 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种纳米技术领域的制备可溶于极性溶剂的纳米四氧化三铁颗粒的方法，步骤为：(1)称取FeCl3·6H2O和FeCl2·4H2O，其摩尔比为2∶1，溶于水中，获得铁盐溶液；(2)量筒量取易溶解于非极性溶剂的胺，溶非极性溶剂中，得到胺/非极性溶剂的混合溶；(3)在采用氮气保护的条件下，将铁盐溶液缓慢滴入胺/非极性溶剂的混合溶液中，进行持续反应；(4)取出反应产物后，采用离心方法获得沉淀物，并用丙酮和去离子水清洗，真空冷冻干燥后获得黑色粉末，即为纳米四氧化三铁颗粒。本发明所得颗粒在水和多种极性溶剂中具有良好的分散性，粒径分布较为均一，粒径表面带有一定电荷，利于在其上包裹聚合物，且具有较高的饱和磁化强度和超顺磁性。
A method for preparing nano ferric oxide particles soluble in polar solvents in the field of nanotechnology . : 1, be dissolved in water, obtain iron salt solution; (2) graduated cylinder measures the amine that is easily soluble in nonpolar solvent, dissolves in nonpolar solvent, obtains the mixed solution of amine/nonpolar solvent; (3) in Under the condition of nitrogen protection, the iron salt solution was slowly dropped into the mixed solution of amine/non-polar solvent for continuous reaction; (4) after taking out the reaction product, the precipitate was obtained by centrifugation, and washed with acetone and deionized water After cleaning and vacuum freeze-drying, a black powder is obtained, which is nanometer ferric oxide particles. The particles obtained in the present invention have good dispersibility in water and various polar solvents, the particle size distribution is relatively uniform, and the surface of the particle size has a certain charge, which is beneficial to wrapping polymers on it, and has higher saturation magnetization and superparamagnetic.
Description
技术领域technical field
本发明涉及的是一种纳米技术领域的方法，具体是一种制备可溶于极性溶剂的纳米四氧化三铁颗粒的方法。The invention relates to a method in the field of nanotechnology, in particular to a method for preparing nano ferric oxide particles soluble in polar solvents.
背景技术Background technique
近年来，由于磁性纳米颗粒在实际应用中的广泛前景，有关磁性纳米颗粒的制备方法及性质的研究受到了很大的重视。在磁记录材料方面，磁性纳米颗粒可望取代传统的微米级磁粉，用于高密度磁记录材料；在生物领域，用磁性纳米材料制成的磁性微球可广泛用于磁共振造影成像，药物载体，热疗以及细胞和蛋白质的分离等方面。纳米四氧化三铁颗粒的制备方法有多种，总体上可分为湿法和干法。湿法多以氯化亚铁和氯化铁为原料，采用共沉淀法、水热法、溶胶一凝胶法以及微乳液法制备；干法常以羰基铁[Fe(CO)5]等为原料，采用气相沉积、热分解等方法制备。以上制备方法各有千秋，需求不同，可采用不同的制备方法。In recent years, due to the broad prospects of magnetic nanoparticles in practical applications, the research on the preparation methods and properties of magnetic nanoparticles has received great attention. In terms of magnetic recording materials, magnetic nanoparticles are expected to replace traditional micron-sized magnetic powder for high-density magnetic recording materials; in the biological field, magnetic microspheres made of magnetic nanomaterials can be widely used in magnetic resonance imaging, medicine Carriers, hyperthermia, and separation of cells and proteins. There are many methods for the preparation of nano-Fe3O4 particles, which can be generally divided into wet method and dry method. The wet method mostly uses ferrous chloride and ferric chloride as raw materials, and is prepared by coprecipitation method, hydrothermal method, sol-gel method and microemulsion method; the dry method often uses carbonyl iron [Fe(CO) 5 ], etc. The raw material is prepared by methods such as vapor deposition and thermal decomposition. The above preparation methods have their own advantages and disadvantages, and the requirements are different, so different preparation methods can be used.
经对现有技术的文献检索发现，化学共沉淀法是一种最简单直接的能大量获得纳米四氧化三铁颗粒的方法，如杂志《Advanced Materials》(《先进材料》)2001年第13卷1158页发表题为“Ordered two-dimensional arrays of ferritenanoparticles”(“铁氧体纳米颗粒的二维有序阵列”)的文章，采用氯化亚铁和氯化铁混和溶液，缓慢滴入氨水或氢氧化钠溶液中，而获得四氧化三铁颗粒。这种方法的主要缺点在于：1.水相环境里进行的反应，反应速度快，获得的颗粒大，而且分布不均匀；2.制备的四氧化三铁颗粒带有疏水性表面，在不加入其他表面活性剂或高分子保护的情况下，颗粒极易团聚，很难获得在水中分散良好的颗粒。Found through literature search to prior art, chemical co-precipitation method is a kind of simplest and direct method that can obtain nano ferric oxide particle in a large number, as magazine " Advanced Materials " (" advanced material ") 2001 the thirteenth volumes Published an article entitled "Ordered two-dimensional arrays of ferritenanoparticles" ("two-dimensional ordered array of ferrite nanoparticles") on page 1158, using a mixed solution of ferrous chloride and ferric chloride, slowly dripping ammonia water or hydrogen Sodium oxide solution to obtain ferric oxide particles. The main shortcoming of this method is: 1. the reaction that carries out in the aqueous phase environment, reaction speed is fast, and the particle that obtains is big, and distribution is uneven; In the case of other surfactants or polymer protection, the particles are easy to agglomerate, and it is difficult to obtain well-dispersed particles in water.
发明内容Contents of the invention
本发明针对现有技术中的不足，提供一种制备可溶于极性溶剂的纳米四氧化三铁颗粒的方法，使其在保留原化学共沉淀法能大量制备的优点的同时，生产周期短，能获得高纯度细颗粒分散好的四氧化三铁颗粒。Aiming at the deficiencies in the prior art, the present invention provides a method for preparing nano ferric oxide particles soluble in polar solvents, so that the production cycle is short while retaining the advantages of the original chemical co-precipitation method that can be prepared in large quantities , can obtain ferric oxide particles with high purity fine particle dispersion.
本发明是通过以下技术方案实现的，本发明采用水/油界面上的共沉淀法来制备，包括以下步骤：The present invention is achieved through the following technical solutions, and the present invention adopts the co-precipitation method on the water/oil interface to prepare, comprising the following steps:
(1)称取FeCl3·6H2O和FeCl2·4H2O，其摩尔比为2∶1，溶于10～1000ml水中，获得铁盐溶液；(1) Weigh FeCl 3 6H 2 O and FeCl 2 4H 2 O, the molar ratio of which is 2:1, dissolve in 10-1000ml of water to obtain an iron salt solution;
(2)量筒量取2～50ml易溶解于非极性溶剂的油溶性的胺，溶于30～1000ml非极性溶剂中，得到胺/非极性溶剂的混合溶；(2) Measure 2-50ml of oil-soluble amines easily soluble in non-polar solvents in a graduated cylinder, and dissolve them in 30-1000ml of non-polar solvents to obtain a mixed solution of amine/non-polar solvents;
(3)在采用氮气保护的条件下，将铁盐溶液缓慢滴入胺/非极性溶剂的混合溶液中，温度控制在20～80℃之间，反应持续0.5～12小时；(3) Under the condition of nitrogen protection, the iron salt solution is slowly dropped into the mixed solution of amine/non-polar solvent, the temperature is controlled between 20-80°C, and the reaction lasts for 0.5-12 hours;
(4)取出反应产物后采用离心方法(11000转/分的转速离心10分钟)获得沉淀物，并用丙酮和去离子水清洗1～10次，真空冷冻干燥12～24小时后获得黑色粉末，即为纳米四氧化三铁颗粒。(4) After taking out the reaction product, adopt centrifugation (11000 rev/min speed centrifugation for 10 minutes) to obtain the precipitate, and wash 1 to 10 times with acetone and deionized water, and obtain a black powder after vacuum freeze-drying for 12 to 24 hours, namely It is nano ferric oxide particles.
本发明中，Fe3+和Fe2+最适宜浓度分别为0.05～0.2mol/l和0.025~0.1mol/l，胺/非极性溶剂的混合溶液用量最适宜为5ml/50ml，反应温度最适宜为25℃～50℃，反应时间最适宜为0.5～3小时。In the present invention, the optimal concentrations of Fe 3+ and Fe 2+ are respectively 0.05～0.2mol/l and 0.025～0.1mol/l, the optimum dosage of the mixed solution of amine/nonpolar solvent is 5ml/50ml, and the optimum reaction temperature The suitable temperature is 25° C. to 50° C., and the most suitable reaction time is 0.5 to 3 hours.
本发明中，非极性溶剂最适宜的种类为六～八个碳原子的烷烃，油溶性的胺为含六～八个碳原子的有机胺类。In the present invention, the most suitable type of nonpolar solvent is alkanes with six to eight carbon atoms, and the oil-soluble amines are organic amines with six to eight carbon atoms.
本发明采用易溶于非极性溶剂的胺类的油性溶液代替原化学共沉淀方法中的氨水或氢氧化钠，共沉淀反应在水/油界面上进行，从而在保留原化学共沉淀法能大量制备的优点的同时，能产生如下两个特点：通过扩散速度的减慢而使反应速度降低，从而获得较细(粒径约10nm)的分布较均一的颗粒；反应的产物季胺盐类吸附在纳米四氧化三铁表面，使表面带有一定电荷，使颗粒间相互排斥，从而获得分散良好的颗粒，这种颗粒在水和多种极性溶剂中具有良好的分散性，粒径分布较为均一，粒径表面带有一定电荷，利于在其上包裹聚合物，且具有较高的饱和磁化强度和超顺磁性，具有很广阔的生物医用前景。The present invention adopts the oily solution of amines easily soluble in nonpolar solvents to replace ammonia or sodium hydroxide in the original chemical coprecipitation method, and the coprecipitation reaction is carried out on the water/oil interface, thereby retaining the energy of the original chemical coprecipitation method At the same time as the advantages of mass production, the following two characteristics can be produced: the reaction rate is reduced by slowing down the diffusion rate, thereby obtaining finer (particle size about 10nm) particles with a more uniform distribution; the reaction product quaternary ammonium salts Adsorbed on the surface of nanometer ferric oxide, so that the surface has a certain charge, so that the particles repel each other, so as to obtain well-dispersed particles. This kind of particles has good dispersibility in water and various polar solvents, and the particle size distribution It is relatively uniform, and the surface of the particle size has a certain charge, which is conducive to wrapping polymers on it, and has high saturation magnetization and superparamagnetism, and has broad biomedical prospects.
与现有技术相比，本发明有诸多优点：1.在常温常压下不使用任何催化剂即可反应；2.反应工艺流程简单，容易建立连续式生产方式，而且生产周期短；3.能大量制备高纯度细颗粒分散好的四氧化三铁颗粒。Compared with the prior art, the present invention has many advantages: 1. It can react without using any catalyst at normal temperature and pressure; 2. The reaction process is simple, it is easy to establish a continuous production mode, and the production cycle is short; 3. It can A large amount of high-purity fine-particle dispersed iron ferric oxide particles are prepared.
附图说明Description of drawings
图1为本发明制备的颗粒的透射电镜观察图Fig. 1 is the transmission electron microscope observation figure of the particle prepared by the present invention
具体实施方式Detailed ways
实施例一：Embodiment one:
称取0.05molFeCl3·6H2O和0.025molFeCl2·4H2O，溶于10ml水中，获得铁盐溶液，量筒量取2ml二异丙胺，溶于30ml正己烷中。在采用氮气保护的条件下，将铁盐的水溶液缓慢滴入二异丙胺/正己烷溶液中，温度控制在25℃，整个反应持续1小时。取出反应产物后采用离心方法(11000转/分，10分钟)用丙酮清洗1次，真空冷冻干燥12小时后获得黑色粉末，即为纳米四氧化三铁颗粒。Weigh 0.05mol FeCl 3 ·6H 2 O and 0.025mol FeCl 2 ·4H 2 O, dissolve in 10ml of water to obtain an iron salt solution, measure 2ml of diisopropylamine in a graduated cylinder, and dissolve in 30ml of n-hexane. Under the condition of nitrogen protection, the aqueous solution of the iron salt was slowly dropped into the diisopropylamine/n-hexane solution, the temperature was controlled at 25° C., and the whole reaction lasted for 1 hour. After the reaction product was taken out, the reaction product was washed once with acetone by centrifugation (11,000 rpm, 10 minutes), and the black powder was obtained after vacuum freeze-drying for 12 hours, which was nanometer ferric oxide particles.
获得的黑色粉末采用X射线衍射(XRD)方法可确定为反尖晶石结构的四氧化三铁颗粒，而且其纯度很高。The obtained black powder can be determined as ferric oxide particles with inverse spinel structure by X-ray diffraction (XRD), and its purity is very high.
采用透射电镜观察所制备的颗粒，如图1所示，可见所制备的四氧化三铁颗粒为近球形，分散良好，粒度分布窄，大小约为10±5nm。Observing the prepared particles with a transmission electron microscope, as shown in Figure 1, it can be seen that the prepared ferric oxide particles are nearly spherical, well dispersed, and the particle size distribution is narrow, with a size of about 10 ± 5nm.
采用傅立叶转换红外光谱(FTIR)、X射线光电子能谱(XPS)以及表面Zeta电位仪测定制备的纳米颗粒表面状态，可以证实，反应产物季胺盐很好的附着在制备的四氧化三铁纳米颗粒表面，表面带有一定正电荷。Using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Surface Zeta Potential Instrument to measure the surface state of the prepared nanoparticles, it can be confirmed that the reaction product quaternary ammonium salt is well attached to the prepared ferric iron tetroxide nanoparticles. The surface of the particle has a certain positive charge on the surface.
采用振动样品磁强计(VSM)和超导量子干涉仪(SQUID)测定获得四氧化三铁颗粒的磁性能，其饱和磁化强度约为50emu/g，矫顽力为零，不同温度下磁化强度变化与绝对温度(K)成正比，从而确定其具有超顺磁性。Vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) were used to measure the magnetic properties of ferric oxide particles. The saturation magnetization is about 50emu/g, the coercive force is zero, and the magnetization at different temperatures The change is proportional to the absolute temperature (K), thus confirming its superparamagnetism.
实施例二：Embodiment two:
称取0.05molFeCl3·6H2O和0.025molFeCl2·4H2O，溶于100ml水中，获得铁盐溶液，量筒量取10ml二异丁胺，溶于300ml正庚烷中。在采用氮气保护的条件下，将二异丁胺/正庚烷溶液缓慢滴入铁盐的水溶液中，温度控制在50℃，整个反应持续0.5小时。取出反应产物后采用离心方法(11000转/分，10分钟)用丙酮清洗1次，再用去离子水洗涤5次，真空冷冻干燥24小时后获得黑色粉末，即为纳米四氧化三铁颗粒。Weigh 0.05mol FeCl 3 ·6H 2 O and 0.025mol FeCl 2 ·4H 2 O, dissolve in 100ml of water to obtain an iron salt solution, measure 10ml of diisobutylamine in a graduated cylinder, and dissolve in 300ml of n-heptane. Under the condition of nitrogen protection, the diisobutylamine/n-heptane solution was slowly dropped into the aqueous solution of iron salt, the temperature was controlled at 50°C, and the whole reaction lasted for 0.5 hours. After the reaction product was taken out, the reaction product was washed once with acetone by centrifugation (11000 rpm, 10 minutes), then washed five times with deionized water, and then vacuum freeze-dried for 24 hours to obtain a black powder, which was nanometer ferric oxide particles.
获得的黑色粉末采用X射线衍射(XRD)方法可确定为反尖晶石结构的四氧化三铁颗粒，而且其纯度很高。The obtained black powder can be determined as ferric oxide particles with inverse spinel structure by X-ray diffraction (XRD), and its purity is very high.
采用透射电镜观察所制备的颗粒，可见所制备的四氧化三铁颗粒为近球形，分散良好，粒度分布窄，大小约为12±5nm。Observing the prepared particles with a transmission electron microscope, it can be seen that the prepared ferric iron tetroxide particles are nearly spherical, well dispersed, and have a narrow particle size distribution, with a size of about 12±5nm.
采用傅立叶转换红外光谱(FTIR)、X射线光电子能谱(XPS)以及表面Zeta电位仪测定制备的纳米颗粒表面状态，可以证实，反应产物季胺盐很好的附着在制备的四氧化三铁纳米颗粒表面，表面带有一定正电荷。Using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Surface Zeta Potential Instrument to measure the surface state of the prepared nanoparticles, it can be confirmed that the reaction product quaternary ammonium salt is well attached to the prepared ferric iron tetroxide nanoparticles. The surface of the particle has a certain positive charge on the surface.
采用振动样品磁强计(VSM)和超导量子干涉仪(SQUID)测定获得四氧化三铁颗粒的磁性能，其饱和磁化强度约为58emu/g，矫顽力为零，不同温度下磁化强度变化与绝对温度(K)成正比，从而确定其具有超顺磁性。Vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) were used to measure the magnetic properties of ferric oxide particles. The saturation magnetization is about 58emu/g, the coercive force is zero, and the magnetization at different temperatures The change is proportional to the absolute temperature (K), thus confirming its superparamagnetism.
实施例三：Embodiment three:
称取0.2molFeCl3·6H2O和0.1molFeCl2·4H2O，溶于100ml水中，获得铁盐溶液，量筒量取50ml二正丁胺，溶于1000ml正己烷中。在采用氮气保护的条件下，将二正丁胺/正己烷溶液缓慢滴入铁盐的水溶液中，温度控制在60℃，整个反应持续10小时。取出反应产物后采用离心方法(11000转/分，10分钟)用丙酮清洗5次，再用去离子水洗涤5次，真空冷冻干燥18小时后获得黑色粉末，即为纳米四氧化三铁颗粒。Weigh 0.2mol FeCl 3 ·6H 2 O and 0.1mol FeCl 2 ·4H 2 O, dissolve in 100ml of water to obtain an iron salt solution, measure 50ml of di-n-butylamine in a graduated cylinder, and dissolve in 1000ml of n-hexane. Under the condition of nitrogen protection, the di-n-butylamine/n-hexane solution was slowly dropped into the aqueous solution of iron salt, the temperature was controlled at 60° C., and the whole reaction lasted for 10 hours. After taking out the reaction product, adopt centrifugation method (11000 rev/min, 10 minutes) to wash 5 times with acetone, then wash 5 times with deionized water, obtain black powder after 18 hours of vacuum freeze-drying, be nano ferric oxide particles.
获得的黑色粉末采用X射线衍射(XRD)方法可确定为反尖晶石结构的四氧化三铁颗粒，而且其纯度很高。The obtained black powder can be determined as ferric oxide particles with inverse spinel structure by X-ray diffraction (XRD), and its purity is very high.
采用透射电镜观察所制备的颗粒，可见所制备的四氧化三铁颗粒为近球形，分散良好，粒度分布窄，大小约为13±6nm。Observing the prepared particles with a transmission electron microscope, it can be seen that the prepared ferric iron tetroxide particles are nearly spherical, well dispersed, and have a narrow particle size distribution, with a size of about 13±6nm.
采用傅立叶转换红外光谱(FTIR)、X射线光电子能谱(XPS)以及表面Zeta电位仪测定制备的纳米颗粒表面状态，可以证实，反应产物季胺盐很好的附着在制备的四氧化三铁纳米颗粒表面，表面带有一定正电荷。Using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Surface Zeta Potential Instrument to measure the surface state of the prepared nanoparticles, it can be confirmed that the reaction product quaternary ammonium salt is well attached to the prepared ferric iron tetroxide nanoparticles. The surface of the particle has a certain positive charge on the surface.
采用振动样品磁强计(VSM)和超导量子干涉仪(SQUID)测定获得四氧化三铁颗粒的磁性能，其饱和磁化强度约为64emu/g，矫顽力为零，不同温度下磁化强度变化与绝对温度(K)成正比，从而确定其具有超顺磁性。Vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) were used to measure the magnetic properties of ferric oxide particles. The saturation magnetization is about 64emu/g, the coercive force is zero, and the magnetization at different temperatures The change is proportional to the absolute temperature (K), thus confirming its superparamagnetism.
实施例四：Embodiment four:
称取0.2molFeCl3·6H2O和0.1molFeCl2·4H2O，溶于1000ml水中，获得铁盐溶液，量筒量取50ml二异丁胺，溶于1000ml正辛烷中。在采用氮气保护的条件下，将二异丁胺/正辛烷溶液缓慢滴入铁盐的水溶液中，温度控制在80℃，整个反应持续3小时。取出反应产物后采用离心方法(11000转/分，10分钟)用丙酮清洗5次，再用去离子水洗涤5次，真空冷冻干燥18小时后获得黑色粉末，即为纳米四氧化三铁颗粒。Weigh 0.2mol FeCl 3 ·6H 2 O and 0.1mol FeCl 2 ·4H 2 O, dissolve in 1000ml of water to obtain an iron salt solution, measure 50ml of diisobutylamine in a graduated cylinder, and dissolve in 1000ml of n-octane. Under the condition of nitrogen protection, the diisobutylamine/n-octane solution was slowly dropped into the iron salt aqueous solution, the temperature was controlled at 80° C., and the whole reaction lasted for 3 hours. After taking out the reaction product, adopt centrifugation method (11000 rev/min, 10 minutes) to wash 5 times with acetone, then wash 5 times with deionized water, obtain black powder after 18 hours of vacuum freeze-drying, be nano ferric oxide particles.
获得的黑色粉末采用X射线衍射(XRD)方法可确定为反尖晶石结构的四氧化三铁颗粒，而且其纯度很高。The obtained black powder can be determined as ferric oxide particles with inverse spinel structure by X-ray diffraction (XRD), and its purity is very high.
采用透射电镜观察所制备的颗粒，可见所制备的四氧化三铁颗粒为近球形，分散良好，粒度分布窄，大小约为13±5nm。Observing the prepared particles with a transmission electron microscope, it can be seen that the prepared ferric iron tetroxide particles are nearly spherical, well dispersed, and have a narrow particle size distribution, with a size of about 13±5nm.
采用傅立叶转换红外光谱(FTIR)、X射线光电子能谱(XPS)以及表面Zeta电位仪测定制备的纳米颗粒表面状态，可以证实，反应产物季胺盐很好的附着在制备的四氧化三铁纳米颗粒表面，表面带有一定正电荷。Using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Surface Zeta Potential Instrument to measure the surface state of the prepared nanoparticles, it can be confirmed that the reaction product quaternary ammonium salt is well attached to the prepared ferric iron tetroxide nanoparticles. The surface of the particle has a certain positive charge on the surface.
采用振动样品磁强计(VSM)和超导量子干涉仪(SQUID)测定获得四氧化三铁颗粒的磁性能，其饱和磁化强度约为62emu/g，矫顽力为零，不同温度下磁化强度变化与绝对温度(K)成正比，从而确定其具有超顺磁性。Vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) were used to measure the magnetic properties of ferric oxide particles. The saturation magnetization is about 62emu/g, the coercive force is zero, and the magnetization at different temperatures The change is proportional to the absolute temperature (K), thus confirming its superparamagnetism.
实施例五：Embodiment five:
称取0.1molFeCl3·6H2O和0.05molFeCl2·4H2O，溶于100ml水中，获得铁盐溶液，量筒量取5ml二异丁胺，溶于50ml正辛烷中。在采用氮气保护的条件下，将二异丁胺/正辛烷溶液缓慢滴入铁盐的水溶液中，温度控制在40℃，整个反应持续5小时。取出反应产物后采用离心方法(11000转/分，10分钟)用丙酮清洗5次，再用去离子水洗涤5次，真空冷冻干燥18小时后获得黑色粉末，即为纳米四氧化三铁颗粒。Weigh 0.1mol FeCl 3 ·6H 2 O and 0.05mol FeCl 2 ·4H 2 O, dissolve in 100ml of water to obtain iron salt solution, measure 5ml of diisobutylamine in a graduated cylinder, and dissolve in 50ml of n-octane. Under the condition of nitrogen protection, the diisobutylamine/n-octane solution was slowly dropped into the iron salt aqueous solution, the temperature was controlled at 40°C, and the whole reaction lasted for 5 hours. After taking out the reaction product, adopt centrifugation method (11000 rev/min, 10 minutes) to wash 5 times with acetone, then wash 5 times with deionized water, obtain black powder after 18 hours of vacuum freeze-drying, be nano ferric oxide particles.
获得的黑色粉末采用X射线衍射(XRD)方法可确定为反尖晶石结构的四氧化三铁颗粒，而且其纯度很高。The obtained black powder can be determined as ferric oxide particles with inverse spinel structure by X-ray diffraction (XRD), and its purity is very high.
采用透射电镜观察所制备的颗粒，可见所制备的四氧化三铁颗粒为近球形，分散良好，粒度分布窄，大小约为14±5nm。Observing the prepared particles with a transmission electron microscope, it can be seen that the prepared ferric iron tetroxide particles are nearly spherical, well dispersed, and have a narrow particle size distribution, with a size of about 14±5nm.
采用傅立叶转换红外光谱(FTIR)、X射线光电子能谱(XPS)以及表面Zeta电位仪测定制备的纳米颗粒表面状态，可以证实，反应产物季胺盐很好的附着在制备的四氧化三铁纳米颗粒表面，表面带有一定正电荷。Using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Surface Zeta Potential Instrument to measure the surface state of the prepared nanoparticles, it can be confirmed that the reaction product quaternary ammonium salt is well attached to the prepared ferric iron tetroxide nanoparticles. The surface of the particle has a certain positive charge on the surface.
采用振动样品磁强计(VSM)和超导量子干涉仪(SQUID)测定获得四氧化三铁颗粒的磁性能，其饱和磁化强度约为60emu/g，矫顽力为零，不同温度下磁化强度变化与绝对温度(K)成正比，从而确定其具有超顺磁性。Vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) were used to measure the magnetic properties of ferric oxide particles. The saturation magnetization is about 60emu/g, the coercive force is zero, and the magnetization at different temperatures The change is proportional to the absolute temperature (K), thus confirming its superparamagnetism.
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