CN101289314B - A kind of preparation method of spinel type ferrite nano hollow microsphere - Google Patents

A kind of preparation method of spinel type ferrite nano hollow microsphere Download PDF

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CN101289314B
CN101289314B CN2007100985874A CN200710098587A CN101289314B CN 101289314 B CN101289314 B CN 101289314B CN 2007100985874 A CN2007100985874 A CN 2007100985874A CN 200710098587 A CN200710098587 A CN 200710098587A CN 101289314 B CN101289314 B CN 101289314B
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傅绍云
朱路平
肖红梅
李元庆
杨果
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention provides a preparation method of spinel type ferrite nanometer hollow microspheres, which comprises the following steps: adding a trivalent ferric salt into a glycol solution, and fully stirring to form a first solution; weighing metal salt according to the general formula of the spinel type ferrite, and dissolving the metal salt in the first solution to form a second solution; then, adding ethylenediamine into the second solution to obtain a third solution; then, putting the third solution in a closed reaction container, and preserving heat to obtain a precipitate; and finally, washing and drying the precipitate to obtain the spinel-type ferrite nano hollow microsphere. The spinel-type ferrite nano hollow microspheres prepared by the method provided by the invention have the advantages of good dispersibility, uniform size, regular crystal form, low cost of required raw materials, no need of nitrogen protection in the preparation process, capability of obtaining homogeneous spinel-type ferrite hollow microspheres at a lower temperature (200-250 ℃), simple preparation process, capability of large-scale preparation and suitability for large-scale production.

Description

一种尖晶石型铁氧体纳米空心微球的制备方法 A kind of preparation method of spinel type ferrite nano hollow microsphere

发明领域field of invention

本发明涉及一种尖晶石型铁氧体纳米空心微球的制备方法。The invention relates to a preparation method of spinel type ferrite nano hollow microspheres.

背景技术Background technique

尖晶石型铁氧体是一种重要的软磁材料,其广泛应用于电子器件、信息储存及磁共振成像(MRI)等领域。随着技术的发展,人们发现,当材料尺寸达到纳米尺度时,其常常会表现出与块体材料不同的电、磁、光等性质,因而纳米材料得到了人们越来越多地关注。近年来,纳米磁性材料在磁存储、超流体、药物的磁性传输等方面的实际应用也日益广泛。铁氧体不但被用作传感和成像的靶标,而且其还被广泛用作抗癌治疗的活性剂。例如,日本神户大学医学院采用纳米铁氧体来治疗肝癌,肾癌就取得了较大成功。这表明纳米铁氧体在生物医药方面有着良好的应用前景。因此,合成新型纳米铁氧体磁性材料并对其性能进行研究已成为广泛研究的热点。Spinel ferrite is an important soft magnetic material, which is widely used in electronic devices, information storage and magnetic resonance imaging (MRI) and other fields. With the development of technology, it is found that when the size of the material reaches the nanoscale, it often exhibits different electrical, magnetic, and optical properties from bulk materials, so nanomaterials have attracted more and more attention. In recent years, the practical application of nanomagnetic materials in magnetic storage, superfluid, and magnetic transport of drugs has become increasingly widespread. Ferrites are not only used as targets for sensing and imaging, but they are also widely used as active agents for anticancer therapy. For example, Kobe University School of Medicine in Japan used nano-ferrite to treat liver cancer, and kidney cancer has achieved great success. This shows that nano-ferrite has a good application prospect in biomedicine. Therefore, the synthesis of new nano-ferrite magnetic materials and the study of their properties have become a hotspot of extensive research.

由于特殊的中空结构,纳米铁氧体磁性空心微球有望作为有效的药物传输的载体。目前,无机空心微球的制备通常采用模板方法,即以纳米氧化硅以及聚合物乳胶微球为模板,通过层层静电自组装法、溶胶凝胶法、均匀沉淀法等,将无机物包覆在模板上,然后通过热解或溶解除去模板,从而得到相应的无机空心微球。然而,采用该种方法通常面临成本高、制备过程繁杂等不利因素,难于大量制备和规模化生产。由于制备的特殊难度,单分散的纳米铁氧体磁性空心球的制备研究更是凤毛麟角,如J.Colloid & Interface Sci.2005,281,432(Journal of Colloid and InterfaceScience,281卷,432页,2005年),Chem.Phys.Lett.2006,422,294(Chemistry PhysicsLetters,422卷,294页,2006年)以及J.Am.Chem.Soc.2006,128,8382(Journal ofAmerican Chemistry Society,128卷,8382页,2006年)分别报道了采用模板法和溶剂热法制备了四氧化三铁和系列铁氧体嵌段共聚物空心微球,其中铁氧体嵌段共聚物空心微球的制备是将3.0mmol的三氯化铁,1.5mmol的氯化锰或钴,43.6mmol醋酸钠及0.525mmol的聚氧化乙烯-聚氧化丙烯-聚氧化乙烯嵌段共聚物(PEO-PPO-PEO)溶于35ml乙二醇溶液中,充分搅拌,转入反应釜,并在200℃保温4小时后经离心、醇洗、干燥,得铁氧体(Mn1-xFe2+xO4)/嵌段共聚物异质空心微米球。但制得的产品多为多晶结构且存在表面粗糙、尺寸分布不均匀、空腔不规则等不足。Due to the special hollow structure, nanoferrite magnetic hollow microspheres are expected to be effective carriers for drug delivery. At present, the preparation of inorganic hollow microspheres usually adopts the template method, that is, nano-silica and polymer latex microspheres are used as templates, and the inorganic materials are coated by layer-by-layer electrostatic self-assembly method, sol-gel method, uniform precipitation method, etc. On the template, the template is then removed by pyrolysis or dissolution to obtain the corresponding inorganic hollow microspheres. However, this method usually faces unfavorable factors such as high cost and complicated preparation process, and it is difficult to prepare in large quantities and produce on a large scale. Due to the special difficulty of preparation, the preparation research of monodisperse nano-ferrite magnetic hollow spheres is even rarer, such as J.Colloid & Interface Sci.2005, 281, 432 (Journal of Colloid and Interface Science, volume 281, page 432, 2005 Year), Chem.Phys.Lett.2006, 422, 294 (Chemistry Physics Letters, Volume 422, Page 294, 2006) and J.Am.Chem.Soc.2006, 128, 8382 (Journal of American Chemistry Society, Volume 128, 8382 pages, in 2006) have reported adopting template method and solvothermal method to prepare iron ferrite tetroxide and series ferrite block copolymer hollow microsphere respectively, wherein the preparation of ferrite block copolymer hollow microsphere is the 3.0mmol of ferric chloride, 1.5mmol of manganese chloride or cobalt, 43.6mmol of sodium acetate and 0.525mmol of polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer (PEO-PPO-PEO) are dissolved in 35ml In ethylene glycol solution, fully stirred, transferred to a reaction kettle, and kept at 200°C for 4 hours, then centrifuged, washed with alcohol, and dried to obtain ferrite (Mn 1-x Fe 2+x O 4 )/block copolymer Heterogeneous hollow microspheres. However, most of the products obtained are polycrystalline structures and have shortcomings such as rough surfaces, uneven size distribution, and irregular cavities.

发明内容Contents of the invention

本发明的目的在于克服现有技术制备尖晶石型铁氧体空心微球得到的产品表面粗糙、尺寸分布不均匀、空腔不规则等缺陷,从而提供一种粒径为纳米尺寸、粒度分布均匀的尖晶石型铁氧体纳米空心微球的制备方法。The purpose of the present invention is to overcome defects such as surface roughness, uneven size distribution, and irregular cavities obtained by preparing spinel-type ferrite hollow microspheres in the prior art, thereby providing a nanometer-sized, particle-size-distribution The invention discloses a method for preparing uniform spinel-type ferrite nano hollow microspheres.

本发明的目的是通过如下的技术方案实现的:The purpose of the present invention is achieved through the following technical solutions:

本发明提供了一种尖晶石型铁氧体纳米空心微球的制备方法,该方法包括如下步骤:The invention provides a preparation method of spinel ferrite nano hollow microspheres, the method comprising the following steps:

1)在常温常压下,将三价铁盐加入乙二醇溶液中,充分搅拌形成第一溶液,其中,三价铁盐的浓度为0.05~0.4mol/l;1) Add the ferric salt into the ethylene glycol solution at normal temperature and pressure, and fully stir to form the first solution, wherein the concentration of the ferric salt is 0.05-0.4 mol/l;

2)按照尖晶石型铁氧体通式MxM′yM″(1-x-y)Fe2O4中金属离子M、M′和M″的化学计量比分别称取含M、M′和M″的盐,并在常温常压下将其溶解于步骤1)制备的第一溶液中,充分搅拌形成第二溶液,其中,所述金属离子M,M′和M″分别选自Mn、Zn、Co和Ni的二价离子以及Fe的三价离子,且0<x≤1,0≤y<1,x+y≤1; 2 ) Weigh M , M ' and and M "salt, and under normal temperature and pressure, it is dissolved in the first solution prepared in step 1), fully stirred to form a second solution, wherein, the metal ions M, M' and M" are respectively selected from Mn , Zn, Co and Ni divalent ions and Fe trivalent ions, and 0<x≤1, 0≤y<1, x+y≤1;

3)然后,在常温常压下,将乙二胺加入到步骤2)制备的第二溶液中,充分搅拌得到第三溶液,其中,乙二胺与乙二醇的体积比为0.05~0.35∶1;3) Then, under normal temperature and pressure, ethylenediamine is added to the second solution prepared in step 2), and fully stirred to obtain a third solution, wherein the volume ratio of ethylenediamine to ethylene glycol is 0.05 to 0.35: 1;

4)接着,将步骤3)制备的第三溶液置于密闭的反应容器中,在200-250℃下,保温8~12小时,得到沉淀;4) Next, place the third solution prepared in step 3) in a closed reaction vessel, and keep it warm for 8-12 hours at 200-250° C. to obtain a precipitate;

5)最后,将上述步骤4)得到的沉淀用去离子水洗涤、干燥,即制得尖晶石型铁氧体纳米空心微球。5) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain spinel-type ferrite hollow nanospheres.

在本发明的一个实施方案中,所述M、M′和M″的盐优选为含Co、Mn、Zn或Ni的二价盐,或者为三价铁盐。In one embodiment of the present invention, the salts of M, M' and M" are preferably divalent salts containing Co, Mn, Zn or Ni, or ferric salts.

在本发明的另一个实施方案中,所述的含Mn的二价盐优选为Mn(NO3)2,MnCl2,MnSO4,Mn(CH3COO)2及其混合物。In another embodiment of the present invention, the said divalent salt containing Mn is preferably Mn(NO 3 ) 2 , MnCl 2 , MnSO 4 , Mn(CH 3 COO) 2 and mixtures thereof.

在本发明的又一个实施方案中,所述的含Zn的二价盐优选为Zn(NO3)2,ZnCl2,ZnSO4,Zn(CH3COO)2及其混合物。In yet another embodiment of the present invention, the Zn-containing divalent salt is preferably Zn(NO 3 ) 2 , ZnCl 2 , ZnSO 4 , Zn(CH 3 COO) 2 and mixtures thereof.

在本发明的再一个实施方案中,所述的含Co的二价盐优选为Co(NO3)2,CoCl2,CoSO4,Co(CH3COO)2及其混合物。In yet another embodiment of the present invention, the said divalent salt containing Co is preferably Co(NO 3 ) 2 , CoCl 2 , CoSO 4 , Co(CH 3 COO) 2 and mixtures thereof.

在本发明的再一个实施方案中,所述的含Ni的二价盐优选为Ni(NO3)2,NiCl2,NiSO4,Ni(CH3COO)2及其混合物。In yet another embodiment of the present invention, the Ni-containing divalent salt is preferably Ni(NO 3 ) 2 , NiCl 2 , NiSO 4 , Ni(CH 3 COO) 2 and mixtures thereof.

在本发明的再一个实施方案中,所述三价铁盐优选为FeCl3,Fe(NO3)3,Fe2(SO4)3及其混合物。In yet another embodiment of the present invention, the ferric salt is preferably FeCl 3 , Fe(NO 3 ) 3 , Fe 2 (SO 4 ) 3 and mixtures thereof.

由本发明提供的制备方法得到的尖晶石型铁氧体纳米空心微球,其尺寸在200~300nm,壁厚在20~40nm。The spinel type ferrite nano hollow microsphere obtained by the preparation method provided by the invention has a size of 200-300nm and a wall thickness of 20-40nm.

与现有技术相比,本发明提供的尖晶石型铁氧体纳米空心微球的制备方法具有如下优点:Compared with the prior art, the preparation method of the spinel ferrite nano hollow microspheres provided by the present invention has the following advantages:

1、本发明提供的方法制备得到的尖晶石型铁氧体纳米空心微球分散性好,尺寸均匀,尺寸在200~300nm,壁厚在20~40nm;1. The spinel-type ferrite nano hollow microspheres prepared by the method provided by the present invention have good dispersibility, uniform size, the size is 200-300nm, and the wall thickness is 20-40nm;

2、本发明提供的方法制备得到的尖晶石型铁氧体纳米空心微球晶型规整,是均相无杂质的单晶尖晶石型铁氧体;2. The spinel-type ferrite nano-hollow microspheres prepared by the method provided by the present invention have a regular crystal form and are homogeneous single-crystal spinel-type ferrite without impurities;

3、本发明提供的制备方法所需的原材料成本低廉;3. The cost of raw materials required by the preparation method provided by the invention is low;

4、本发明提供的整个制备过程均在空气条件下进行,无需氮气保护;4. The whole preparation process provided by the present invention is carried out under air conditions without nitrogen protection;

5、本发明提供的制备方法中,铁氧体的制备在较低温度(200~250℃)下溶剂热处理即可得到均相的尖晶石型铁氧体空心微球;5. In the preparation method provided by the present invention, homogeneous spinel-type ferrite hollow microspheres can be obtained by solvent heat treatment at a relatively low temperature (200-250° C.) for the preparation of ferrite;

6、本发明提供的制备方法工艺简单,可大量制备,适于规模化生产。6. The preparation method provided by the present invention has a simple process, can be prepared in large quantities, and is suitable for large-scale production.

附图说明Description of drawings

图1为实施例1制得的四氧化三铁纳米空心微球的扫描电镜(SEM)照片;Fig. 1 is the scanning electron microscope (SEM) photo of the iron ferric oxide nano hollow microspheres that embodiment 1 makes;

图2为实施例1制得的四氧化三铁纳米空心微球的电子能谱图(EDX);图3为实施例2制得的钴铁氧体纳米空心微球的透射电镜(TEM)照片;Fig. 2 is the electron energy spectrum (EDX) of the iron ferrite nano-hollow microspheres that embodiment 1 makes; Fig. 3 is the transmission electron microscope (TEM) photograph of the cobalt ferrite nano-hollow microspheres that embodiment 2 makes ;

图4为实施例2制得的钴铁氧体纳米空心微球的电子衍射图(ED);Fig. 4 is the electron diffraction figure (ED) of the cobalt ferrite nano hollow microsphere that embodiment 2 makes;

图5为实施例3、5、11和15制得的MnFe2O4、CoFe2O4、Mn0.5Zn0.5Fe2O4、Co0.5Ni0.5Fe2O4纳米空心微球的的X射线衍射谱图(XRD)。Fig. 5 is the X-ray of MnFe 2 O 4 , CoFe 2 O 4 , Mn 0.5 Zn 0.5 Fe 2 O 4 , Co 0.5 Ni 0.5 Fe 2 O 4 nano hollow microspheres prepared in Examples 3, 5, 11 and 15 Diffraction pattern (XRD).

具体实施方式Detailed ways

以下结合附图和实施例进一步阐述本发明,但这些实施例仅限于说明本发明而不用于限制本发明的范围。本发明的保护范围以所附的权利要求书为准。The present invention will be further described below in conjunction with the accompanying drawings and examples, but these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The protection scope of the present invention shall be determined by the appended claims.

实施例1Example 1

本实施例制备单分散四氧化三铁纳米空心微球,步骤和条件如下:This embodiment prepares monodisperse ferric oxide nano hollow microspheres, the steps and conditions are as follows:

1)将适量FeCl3溶于40ml乙二醇,充分搅拌形成FeCl3浓度为0.4mol/l的澄清溶液,即第一溶液;1) Dissolve an appropriate amount of FeCl3 in 40ml of ethylene glycol, and fully stir to form a clear solution with a FeCl3 concentration of 0.4mol/l, that is, the first solution;

2)将Fe(NO3)3按照摩尔比Fe(NO3)3:FeCl3=1:2加入到第一溶液中,充分搅拌形成第二溶液;2) Fe(NO 3 ) 3 is added into the first solution according to the molar ratio of Fe(NO 3 ) 3 :FeCl 3 =1:2, and fully stirred to form the second solution;

3)将乙二胺逐滴滴加到第二溶液中,其加入量与乙二醇的体积比为0.2:1,充分搅拌形成即第三溶液;3) Add ethylenediamine dropwise to the second solution, the volume ratio of the added amount to ethylene glycol is 0.2:1, and fully stir to form the third solution;

4)将上述所得的第三溶液转到密闭的反应容器中,在200℃的条件下,保温8小时,得到沉淀;4) Transfer the third solution obtained above into a closed reaction vessel, and keep it warm for 8 hours under the condition of 200° C. to obtain a precipitate;

5)最后,将上述步骤4)得到的沉淀用去离子水洗涤、干燥,即制得单分散的四氧化三铁纳米空心微球。5) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain monodisperse iron ferric oxide hollow nanospheres.

上述第一、第二、和第三溶液的配制都是在常温常压下进行的。The preparation of the first, second, and third solutions above is all carried out at normal temperature and pressure.

本实施例制备的四氧化三铁纳米空心微球的电子显微镜扫描照片和电子能谱图分别如图1和图2所示,从图1中可以看出制得的样品表面较为光滑,且分散性好,粒径均匀,尺寸在200~300nm,壁厚在20~40nm,部分破的球体呈现出半球形及碗形,证明制得的样品具有中空结构;从图2中可以看出制得的样品仅含有Fe和O两种元素(其中Au为导电需要,制样时所喷之金),且根据电子能谱数据可知,元素个数Fe/O~3/4,初步证明制得样品为Fe3O4The electron microscope scanning photo and the electron energy spectrum of the ferroferric oxide nano hollow microspheres prepared in this example are shown in Figure 1 and Figure 2 respectively. Good performance, uniform particle size, size 200-300nm, wall thickness 20-40nm, partially broken spheres present a hemispherical and bowl shape, proving that the prepared sample has a hollow structure; it can be seen from Figure 2 that the prepared The sample contained only two elements, Fe and O (among which Au is required for electrical conductivity, and the gold was sprayed during sample preparation), and according to the electron spectrum data, the number of elements was Fe/O~3/4, which preliminarily proved that the prepared sample is Fe 3 O 4 .

实施例2Example 2

本实施例中除了步骤1)使用硝酸铁(Fe(NO3)3)或硫酸铁(Fe2(SO4)3)替代氯化铁(FeCl3)外,其他步骤和条件都与实施例1相同,同样可以得到单晶、单分散四氧化三铁纳米空心微球。In this example, except that step 1) uses iron nitrate (Fe(NO 3 ) 3 ) or iron sulfate (Fe 2 (SO 4 ) 3 ) instead of iron chloride (FeCl 3 ), other steps and conditions are the same as in Example 1. Similarly, single crystal, monodisperse ferric oxide nano hollow microspheres can also be obtained.

实施例3Example 3

本实施例制备单分散CoFe2O4铁氧体纳米空心微球,其步骤和条件如下:This example prepares monodisperse CoFe 2 O 4 ferrite nano hollow microspheres, the steps and conditions are as follows:

1)将适量Fe2(SO4)3溶于40ml乙二醇,充分搅拌形成Fe2(SO4)3浓度为0.05mol/l的第一溶液;1) Dissolving an appropriate amount of Fe 2 (SO 4 ) 3 in 40 ml of ethylene glycol, and fully stirring to form a first solution with a Fe 2 (SO 4 ) 3 concentration of 0.05 mol/l;

2)将Co(NO3)2按照化学计量比Co2+:Fe3+=1:2加入到第一溶液中,充分搅拌形成第二溶液;2) Adding Co(NO 3 ) 2 into the first solution according to the stoichiometric ratio Co 2+ : Fe 3+ =1:2, and fully stirring to form the second solution;

3)将乙二胺逐滴滴加到第二溶液中,其加入量与乙二醇的体积比为0.35:1,充分搅拌形成第三溶液;3) Add ethylenediamine dropwise to the second solution, the volume ratio of the added amount to ethylene glycol is 0.35:1, and fully stir to form the third solution;

4)将上述所得的第三溶液转到密闭的反应容器中,在250℃的条件下,保温12小时,得到沉淀;4) Transfer the third solution obtained above into a closed reaction vessel, and keep it warm for 12 hours under the condition of 250° C. to obtain a precipitate;

5)最后,将上述步骤4)得到的沉淀用去离子水洗涤、干燥,即制得单分散的CoFe2O4铁氧体纳米空心微球。5) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain monodisperse CoFe 2 O 4 hollow ferrite nanospheres.

上述第一、第二和第三溶液的配制都是在常温常压下进行的。The preparation of the above-mentioned first, second and third solutions is all carried out at normal temperature and pressure.

本实施例制备的CoFe2O4铁氧体纳米空心微球的透射电镜(TEM)照片和电子衍射图(ED)分别如图3和图4所示,从图3中可以看出制得的产品边缘和中心部分具有明显的对比度,其中边缘颜色较深,中心部分颜色较浅,这表明制得的样品具有中空结构,分散性好,粒径均匀,尺寸在200~300nm,壁厚在20~40nm;从图4中可以看出样品呈现出典型的单晶衍射花纹,表明制得的样品具有单晶特性。The CoFe 2 O 4 ferrite nano hollow microspheres prepared by the present embodiment are shown in Fig. 3 and Fig. 4 respectively for the transmission electron microscope (TEM) photo and the electron diffraction pattern (ED), as can be seen from Fig. 3 There is a clear contrast between the edge and the center of the product, where the edge is darker and the center is lighter, which indicates that the prepared sample has a hollow structure, good dispersion, uniform particle size, a size of 200-300nm, and a wall thickness of 20 ~40nm; It can be seen from Figure 4 that the sample presents a typical single crystal diffraction pattern, indicating that the prepared sample has single crystal characteristics.

实施例4Example 4

本实施例中除步骤1)中增加Fe2(SO4)3的浓度至0.4mol/l,同时将步骤3)中乙二胺与乙二醇体积比降低至0.05:1外,其他条件和步骤与实施例3相同,同样可以得到单分散CoFe2O4铁氧体纳米空心微球。In this example, in addition to increasing the concentration of Fe 2 (SO 4 ) 3 to 0.4 mol/l in step 1), and reducing the volume ratio of ethylenediamine to ethylene glycol in step 3) to 0.05:1, other conditions and The steps are the same as in Example 3, and monodisperse CoFe 2 O 4 ferrite hollow nanospheres can also be obtained.

实施例5Example 5

本实施例中除步骤2)使用MnCl2替代Co(NO3)2外,其他步骤和条件与实施例3相同,可以得到单晶、单分散的MnFe2O4铁氧体纳米空心微球。In this example, except that step 2) uses MnCl 2 instead of Co(NO 3 ) 2 , other steps and conditions are the same as in Example 3, and single crystal, monodisperse MnFe 2 O 4 ferrite hollow nanospheres can be obtained.

实施例6Example 6

本实施例中除步骤2)使用ZnSO4替代Co(NO3)2外,其他步骤和条件与实施例3相同,可以得到单晶、单分散的ZnFe2O4铁氧体纳米空心微球。In this example, except that step 2) uses ZnSO 4 instead of Co(NO 3 ) 2 , other steps and conditions are the same as in Example 3, and single crystal, monodisperse ZnFe 2 O 4 ferrite hollow nanospheres can be obtained.

实施例7Example 7

本实施例中除步骤2)使用Ni(CH3COO)2替代Co(NO3)2外,其他步骤和条件与实施例3相同,可以得到单晶、单分散的NiFe2O4铁氧体纳米空心微球。In this example, except that step 2) uses Ni(CH 3 COO) 2 instead of Co(NO 3 ) 2 , other steps and conditions are the same as in Example 3, and single crystal, monodisperse NiFe 2 O 4 ferrite can be obtained nano hollow microspheres.

实施例8Example 8

本实施例制备单分散Mn0.5Zn0.5Fe2O4铁氧体纳米空心微球,其步骤和条件如下:This example prepares monodisperse Mn 0.5 Zn 0.5 Fe 2 O 4 ferrite nano hollow microspheres, the steps and conditions are as follows:

1)将适量Fe(NO3)3溶于40ml乙二醇,充分搅拌形成Fe(NO3)3浓度为0.2mol/l的第一溶液;1) Dissolve an appropriate amount of Fe(NO 3 ) 3 in 40ml of ethylene glycol, and stir thoroughly to form a first solution with a Fe(NO 3 ) 3 concentration of 0.2 mol/l;

2)将Mn(NO3)2和ZnSO4按照化学计量比Mn2+:Zn2+:Fe3+=0.5:0.5:2;加入到第一溶液中,充分搅拌形成第二溶液;2) Mn(NO 3 ) 2 and ZnSO 4 are added to the first solution according to the stoichiometric ratio Mn 2+ : Zn 2 + : Fe 3+ =0.5:0.5:2, and fully stirred to form the second solution;

3)将乙二胺逐滴滴加到第二溶液中,其加入量与乙二醇的体积比为0.1:1,充分搅拌形成第三溶液;3) Add ethylenediamine dropwise to the second solution, the volume ratio of the added amount to ethylene glycol is 0.1:1, and fully stir to form the third solution;

4)将上述所得的第三溶液转到密闭的反应容器中,在250℃的条件下,保温10小时,得到沉淀;4) transfer the third solution obtained above into a closed reaction vessel, and keep it warm for 10 hours under the condition of 250° C. to obtain a precipitate;

5)最后,将上述步骤4)得到的沉淀用去离子水洗涤、干燥,即制得单分散的Mn0.5Zn0.5Fe2O4铁氧体纳米空心微球。5) Finally, the precipitate obtained in the above step 4) was washed with deionized water and dried to obtain monodisperse Mn 0.5 Zn 0.5 Fe 2 O 4 ferrite hollow nanospheres.

上述第一、第二和第三溶液的配制都是在常温常压下进行的。The preparation of the above-mentioned first, second and third solutions is all carried out at normal temperature and pressure.

实施例9Example 9

本实施例中除步骤1)增加Fe(NO3)3的浓度至0.4mol/l,同时将步骤3)中乙二胺与乙二醇体积比降低至0.05:1外,其他步骤和条件与实施例8相同,同样可以得到Mn0.5Zn0.5Fe2O4铁氧体纳米空心微球。In this example, except step 1) increasing the concentration of Fe(NO 3 ) 3 to 0.4mol/l, and simultaneously reducing the volume ratio of ethylenediamine to ethylene glycol in step 3) to 0.05:1, other steps and conditions are the same as The same as in Example 8, Mn 0.5 Zn 0.5 Fe 2 O 4 hollow ferrite nanospheres can also be obtained.

实施例10Example 10

本实施例中除步骤1)降低Fe(NO3)3的浓度至0.05mol/l,同时将步骤3)中乙二胺与乙二醇体积比增加至0.35:1外,其他步骤和条件与实施例8相同,同样可以得到Mn0.5Zn0.5Fe2O4铁氧体纳米空心微球。In this example, except that step 1) reduces the concentration of Fe(NO 3 ) 3 to 0.05 mol/l, and at the same time increases the volume ratio of ethylenediamine to ethylene glycol in step 3) to 0.35:1, other steps and conditions are the same as The same as in Example 8, Mn 0.5 Zn 0.5 Fe 2 O 4 hollow ferrite nanospheres can also be obtained.

实施例11Example 11

本实施例中除步骤2)中加入的Mn(NO3)2和ZnSO4分别被NiCl2和CoSO4替代外,其他条件和步骤与实施例8相同,同样也得到Mn0.5Zn0.5Fe2O4铁氧体纳米空心微球。In this example, except that Mn(NO 3 ) 2 and ZnSO 4 added in step 2) are replaced by NiCl 2 and CoSO 4 respectively, other conditions and steps are the same as in Example 8, and Mn 0.5 Zn 0.5 Fe 2 O is also obtained 4 ferrite nano hollow microspheres.

实施例12Example 12

本实施例中除步骤2)中加入的Mn(NO3)2和ZnSO4分别被Co(NO3)2和ZnCl2替代外,其他条件和步骤与实施例8相同,同样也得到Co0.5Zn0.5Fe2O4铁氧体纳米空心微球。In this example, except that Mn(NO 3 ) 2 and ZnSO 4 added in step 2) are replaced by Co(NO 3 ) 2 and ZnCl 2 respectively, other conditions and steps are the same as in Example 8, and Co 0.5 Zn 0.5 Fe 2 O 4 ferrite nano hollow microspheres.

实施例13Example 13

本实施例中除步骤2)中加入的Mn(NO3)2和ZnSO4分别被MnSO4和CoCl2替代外,其他条件和步骤与实施例8相同,同样也得到Mn0.5Co0.5Fe2O4铁氧体纳米空心微球。In this example, except that Mn(NO 3 ) 2 and ZnSO 4 added in step 2) are replaced by MnSO 4 and CoCl 2 respectively, other conditions and steps are the same as in Example 8, and Mn 0.5 Co 0.5 Fe 2 O is also obtained 4 ferrite nano hollow microspheres.

实施例14Example 14

本实施例中除步骤2)中加入的Mn(NO3)2和ZnSO4分别被NiSO4和Zn(NO3)2替代外,其他条件和步骤与实施例8相同,同样也得到Ni0.5Zn0.5Fe2O4铁氧体纳米空心微球。In this example, except that Mn(NO 3 ) 2 and ZnSO 4 added in step 2) are replaced by NiSO 4 and Zn(NO 3 ) 2 respectively, other conditions and steps are the same as in Example 8, and Ni 0.5 Zn 0.5 Fe 2 O 4 ferrite nano hollow microspheres.

实施例15Example 15

本实施例中除步骤2)中加入的Mn(NO3)2和ZnSO4分别被Co(CH3COO)2和Ni(CH3COO)2替代外,其他条件和步骤与实施例8相同,同样也得到Co0.5Ni0.5Fe2O4铁氧体纳米空心微球。In this example, except that Mn(NO 3 ) 2 and ZnSO 4 added in step 2) are replaced by Co(CH 3 COO) 2 and Ni(CH 3 COO) 2 respectively, other conditions and steps are the same as in Example 8, Also obtained Co 0.5 Ni 0.5 Fe 2 O 4 ferrite nano hollow microspheres.

实施例16Example 16

本实施例中除步骤2)中加入的Mn(NO3)2和NiSO4分别被Mn(CH3COO)2和Ni(NO3)2替代外,其他条件和步骤与实施例8相同,同样也得到Mn0.5Ni0.5Fe2O4铁氧体纳米空心微球。In this example, except that Mn(NO 3 ) 2 and NiSO 4 added in step 2) are replaced by Mn(CH 3 COO) 2 and Ni(NO 3 ) 2 respectively, other conditions and steps are the same as in Example 8, and the same Mn 0.5 Ni 0.5 Fe 2 O 4 ferrite nano hollow microspheres were also obtained.

图5给出了实施例3,5,11,15制得的CoFe2O4、MnFe2O4、Mn0.5Zn0.5Fe2O4、Co0.5Ni0.5Fe2O4纳米空心微球的的X射线衍射谱图(XRD),从图中可以看出制得的样品纯相的立方结构的尖晶石型铁氧体,且衍射峰的强度较高,表明制得的样品具有高的晶化度,晶形较为完整。Figure 5 shows the properties of CoFe 2 O 4 , MnFe 2 O 4 , Mn 0.5 Zn 0.5 Fe 2 O 4 , Co 0.5 Ni 0.5 Fe 2 O 4 hollow nanospheres prepared in Examples 3, 5, 11, and 15. X-ray diffraction spectrum (XRD), as can be seen from the figure the spinel ferrite of the cubic structure of the pure phase of the sample made, and the intensity of the diffraction peak is higher, shows that the sample made has high crystallinity The degree of crystallization is relatively complete.

实施例17Example 17

本实施例制备单分散Co0.4Mn0.4Zn0.2Fe2O4铁氧体纳米空心微球,其步骤和条件如下:This example prepares monodisperse Co 0.4 Mn 0.4 Zn 0.2 Fe 2 O 4 hollow ferrite nanospheres, the steps and conditions are as follows:

1)将适量Fe2(SO4)3溶于40ml乙二醇,充分搅拌形成Fe2(SO4)3浓度为0.4mol/l的第一溶液;1) Dissolving an appropriate amount of Fe 2 (SO 4 ) 3 in 40 ml of ethylene glycol, and stirring thoroughly to form a first solution with a Fe 2 (SO 4 ) 3 concentration of 0.4 mol/l;

2)将Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2按照化学计量比Co2+:Mn2+:Zn2+:Fe3+=0.4:0.4:0.2:2加入到第一溶液中,充分搅拌形成第二溶液;2) Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 according to the stoichiometric ratio Co 2+ :Mn 2+ :Zn 2+ :Fe 3+ =0.4:0.4: Add 0.2:2 to the first solution, stir well to form the second solution;

3)将乙二胺逐滴滴加到第二溶液中,其加入量与乙二醇的体积比为0.3:1,充分搅拌形成第三溶液;3) Add ethylenediamine dropwise to the second solution, the volume ratio of the added amount to ethylene glycol is 0.3:1, and fully stir to form the third solution;

4)将上述所得的第三溶液转到密闭的反应容器中,在210℃的条件下,保温11小时,得到沉淀;4) transfer the third solution obtained above into a closed reaction vessel, and keep it warm for 11 hours under the condition of 210° C. to obtain a precipitate;

5)最后,将上述步骤4)得到的沉淀用去离子水洗涤、干燥,即制得单分散的Co0.4Mn0.4Zn0.2Fe2O4铁氧体纳米空心微球。5) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain monodisperse Co 0.4 Mn 0.4 Zn 0.2 Fe 2 O 4 ferrite hollow nanospheres.

上述第一、第二和第三溶液的配制都是在常温常压下进行的。The preparation of the above-mentioned first, second and third solutions is all carried out at normal temperature and pressure.

实施例18Example 18

本实施例中除步骤1)降低Fe2(SO4)3的浓度至0.05mol/l,同时将步骤3)中乙二胺与乙二醇体积比降低至0.05:1外,其他步骤和条件与实施例17相同,同样可以得到Co0.4Mn0.4Zn0.2Fe2O4铁氧体纳米空心微球。In this example, except that step 1) reduces the concentration of Fe 2 (SO 4 ) 3 to 0.05 mol/l, and at the same time reduces the volume ratio of ethylenediamine to ethylene glycol in step 3) to 0.05:1, other steps and conditions Same as in Example 17, Co 0.4 Mn 0.4 Zn 0.2 Fe 2 O 4 hollow ferrite nanospheres can also be obtained.

实施例19Example 19

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被Ni(NO3)2、MnSO4和ZnCl2替代外,其他条件和步骤与实施例17相同,同样也得到Ni0.4Mn0.4Zn0.2Fe2O4铁氧体纳米空心微球。In this example, except that Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) are replaced by Ni(NO 3 ) 2 , MnSO 4 and ZnCl 2 respectively , other conditions and steps were the same as in Example 17, and Ni 0.4 Mn 0.4 Zn 0.2 Fe 2 O 4 ferrite hollow nanospheres were also obtained.

实施例20Example 20

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被Co(NO3)2、NiSO4和ZnCl2替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Ni0.4Zn0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) are replaced by Co(NO 3 ) 2 , NiSO 4 and ZnCl 2 respectively , other conditions and steps were the same as in Example 17, and Co 0.4 Ni 0.4 Zn 0.2 Fe 2 O 4 hollow ferrite nanospheres were also obtained.

实施例21Example 21

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被CoSO4、ZnSO4和MnSO4替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Zn0.4Mn0.2Fe2O4铁氧体纳米空心微球。In this example, except that Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) are replaced by CoSO 4 , ZnSO 4 and MnSO 4 respectively, other conditions and The steps are the same as in Example 17, and Co 0.4 Zn 0.4 Mn 0.2 Fe 2 O 4 hollow ferrite nanospheres are also obtained.

实施例22Example 22

Co0.4Ni0.4Mn0.2Fe2O4 Co 0.4 Ni 0.4 Mn 0.2 Fe 2 O 4

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被CoCl2、NiCl2和Mn(NO3)2、替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Ni0.4Mn0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) were replaced by CoCl 2 , NiCl 2 and Mn(NO 3 ) 2 , respectively. Besides, other conditions and steps were the same as in Example 17, and Co 0.4 Ni 0.4 Mn 0.2 Fe 2 O 4 ferrite hollow nanospheres were also obtained.

实施例23Example 23

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被Zn(NO3)2、Ni(CH3COO)2和MnSO4替代外,其他条件和步骤与实施例17相同,同样也得到Zn0.4Ni0.4Mn0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) were respectively replaced by Zn(NO 3 ) 2 , Ni(CH 3 COO) 2 Except for replacing MnSO 4 , other conditions and steps are the same as in Example 17, and Zn 0.4 Ni 0.4 Mn 0.2 Fe 2 O 4 ferrite hollow nanospheres are also obtained.

实施例24Example 24

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被MnSO4、ZnCl2和Co(NO3)2替代外,其他条件和步骤与实施例17相同,同样也得到Mn0.4Zn0.4Co0.2Fe2O4铁氧体纳米空心微球。In this example, except that Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) are replaced by MnSO 4 , ZnCl 2 and Co(NO 3 ) 2 respectively , other conditions and steps were the same as in Example 17, and Mn 0.4 Zn 0.4 Co 0.2 Fe 2 O 4 ferrite hollow nanospheres were also obtained.

实施例25Example 25

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被MnSO4、Ni(CH3COO)2和CoCl2替代外,其他条件和步骤与实施例17相同,同样也得到Mn0.4Ni0.4Co0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) were replaced by MnSO 4 , Ni(CH 3 COO) 2 and CoCl 2 respectively Besides, other conditions and steps were the same as in Example 17, and Mn 0.4 Ni 0.4 Co 0.2 Fe 2 O 4 ferrite hollow nanospheres were also obtained.

实施例26Example 26

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被Ni(NO3)2、ZnCl2、和CoSO4替代外,其他条件和步骤与实施例17相同,同样也得到Ni0.4Zn0.4Co0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) were replaced by Ni(NO 3 ) 2 , ZnCl 2 , and CoSO 4 respectively Besides, other conditions and steps are the same as in Example 17, and Ni 0.4 Zn 0.4 Co 0.2 Fe 2 O 4 ferrite hollow nanospheres are also obtained.

实施例27Example 27

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被Co(NO3)2、MnSO4和NiCl2替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Mn0.4Ni0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) are replaced by Co(NO 3 ) 2 , MnSO 4 and NiCl 2 respectively , other conditions and steps were the same as in Example 17, and Co 0.4 Mn 0.4 Ni 0.2 Fe 2 O 4 hollow ferrite nanospheres were also obtained.

实施例28Example 28

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被ZnCl2、MnCl2和Ni(CH3COO)2替代外,其他条件和步骤与实施例17相同,同样也得到Zn0.4Mn0.4Ni0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) were replaced by ZnCl 2 , MnCl 2 and Ni(CH 3 COO) 2 respectively In addition, other conditions and steps are the same as in Example 17, and Zn 0.4 Mn 0.4 Ni 0.2 Fe 2 O 4 ferrite hollow nanospheres are also obtained.

实施例29Example 29

本实施例中除步骤2)中加入的Co(CH3COO)2、Mn(CH3COO)2和Zn(CH3COO)2分别被Co(NO3)2、ZnCl2和NiSO4替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Zn0.4Ni0.2Fe2O4铁氧体纳米空心微球。In this example, Co(CH 3 COO) 2 , Mn(CH 3 COO) 2 and Zn(CH 3 COO) 2 added in step 2) are replaced by Co(NO 3 ) 2 , ZnCl 2 and NiSO 4 respectively , other conditions and steps were the same as in Example 17, and Co 0.4 Zn 0.4 Ni 0.2 Fe 2 O 4 hollow ferrite nanospheres were also obtained.

实施例30Example 30

本实施例中除步骤2)中加入的Co(CH3COO)2被Co(NO3)2和CoCl2的混合物替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Zn0.4Ni0.2Fe2O4铁氧体纳米空心微球,其中,Co(NO3)2和CoCl2可以任意比例混合,只要保持第二溶液中各金属离子的化学计量比仍然满足Co2+:Mn2+:Zn2+:Fe3+=0.4:0.4:0.2:2即可。In this example, except that the Co(CH 3 COO) 2 added in step 2) is replaced by a mixture of Co(NO 3 ) 2 and CoCl 2 , other conditions and steps are the same as in Example 17, and Co 0.4 Zn 0.4 is also obtained Ni 0.2 Fe 2 O 4 ferrite nano hollow microspheres, in which Co(NO 3 ) 2 and CoCl 2 can be mixed in any proportion, as long as the stoichiometric ratio of each metal ion in the second solution still satisfies Co 2+ : Mn 2+ : Zn 2+ : Fe 3+ = 0.4: 0.4: 0.2: 2.

实施例31Example 31

本实施例中除步骤2)中加入的Mn(CH3COO)2被MnSO4、Mn(NO3)2和MnCl2的混合物替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Zn0.4Ni0.2Fe2O4铁氧体纳米空心微球,其中,MnSO4、Mn(NO3)2和MnCl2可以任意比例混合,只要保持第二溶液中各金属离子的化学计量比仍然满足Co2+:Mn2+:Zn2+:Fe3+=0.4:0.4:0.2:2即可。In this example, except that the Mn(CH 3 COO) 2 added in step 2) is replaced by a mixture of MnSO 4 , Mn(NO 3 ) 2 and MnCl 2 , other conditions and steps are the same as in Example 17, and Co 0.4 Zn 0.4 Ni 0.2 Fe 2 O 4 ferrite hollow nanospheres, wherein MnSO 4 , Mn(NO 3 ) 2 and MnCl 2 can be mixed in any proportion, as long as the stoichiometric ratio of each metal ion in the second solution remains the same It is sufficient to satisfy Co 2+ : Mn 2+ : Zn 2+ : Fe 3+ =0.4:0.4:0.2:2.

实施例32Example 32

本实施例中除步骤2)中加入的Zn(CH3COO)2被ZnSO4、Zn(CH3COO)2、Zn(NO3)2和ZnCl2的混合物替代外,其他条件和步骤与实施例17相同,同样也得到Co0.4Zn0.4Ni0.2Fe2O4铁氧体纳米空心微球,其中,ZnSO4、Zn(CH3COO)2、Zn(NO3)2和ZnCl2可以任意比例混合,只要保持第二溶液中各金属离子的化学计量比仍然满足Co2+:Mn2+:Zn2+:Fe3+=0.4:0.4:0.2:2即可。In this example, except that the Zn(CH 3 COO) 2 added in step 2) is replaced by a mixture of ZnSO 4 , Zn(CH 3 COO) 2 , Zn(NO 3 ) 2 and ZnCl 2 , other conditions and steps are related to implementation Same as Example 17, Co 0.4 Zn 0.4 Ni 0.2 Fe 2 O 4 ferrite hollow nanospheres are also obtained, wherein ZnSO 4 , Zn(CH 3 COO) 2 , Zn(NO 3 ) 2 and ZnCl 2 can be in any proportion Mixing, as long as the stoichiometric ratio of each metal ion in the second solution still satisfies Co 2+ : Mn 2+ : Zn 2+ : Fe 3+ =0.4:0.4:0.2:2.

实施例33Example 33

本实施例中除步骤1)使用FeCl3和Fe(NO3)3的混合物替代Fe2(SO4)3外,其他其他条件和步骤与实施例17相同,同样也得到Co0.4Zn0.4Ni0.2Fe2O4铁氧体纳米空心微球,其中,FeCl3和Fe(NO3)3的配比可以是任意的,只要保证最终得到的第一溶液中Fe3+的浓度与实施例17中第一溶液中Fe3+的浓度相同即可。In this example, except step 1) using a mixture of FeCl 3 and Fe(NO 3 ) 3 instead of Fe 2 (SO 4 ) 3 , other conditions and steps are the same as in Example 17, and Co 0.4 Zn 0.4 Ni 0.2 is also obtained Fe 2 O 4 ferrite nano hollow microspheres, wherein the ratio of FeCl 3 and Fe(NO 3 ) 3 can be arbitrary, as long as it is ensured that the concentration of Fe 3+ in the first solution finally obtained is the same as that in Example 17 The concentration of Fe 3+ in the first solution should be the same.

以上已结合具体实施方式对本发明作了具体说明,本领域技术人员理解,本发明所述具体实施方式的所有变体、变型、替代方式和等同物均在本发明的范围之内。The present invention has been specifically described above in conjunction with the specific embodiments, and those skilled in the art understand that all variations, modifications, substitutions and equivalents of the specific embodiments of the present invention are within the scope of the present invention.

Claims (7)

1.一种尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,包括如下步骤:1. a preparation method of spinel type ferrite nano hollow microspheres, is characterized in that, comprises the steps: 1)在常温常压下,将三价铁盐加入乙二醇溶液中,充分搅拌形成第一溶液,其中,三价铁盐的浓度为0.05~0.4mol/l;1) Add the ferric salt into the ethylene glycol solution at normal temperature and pressure, and fully stir to form the first solution, wherein the concentration of the ferric salt is 0.05-0.4 mol/l; 2)按照尖晶石型铁氧体通式MxM′yM″(1-x-y)Fe2O4中金属离子M、M′和M″的化学计量比分别称取含M、M′和M″的盐,并在常温常压下将其溶解于步骤1)制备的第一溶液中,充分搅拌形成第二溶液,其中,所述金属离子M,M′和M″分别选自Mn、Zn、Co和Ni的二价离子以及Fe的三价离子,且0<x≤1,0≤y<1,x+y≤1; 2 ) Weigh M , M ' and and M "salt, and under normal temperature and pressure, it is dissolved in the first solution prepared in step 1), fully stirred to form a second solution, wherein, the metal ions M, M' and M" are respectively selected from Mn , Zn, Co and Ni divalent ions and Fe trivalent ions, and 0<x≤1, 0≤y<1, x+y≤1; 3)然后,在常温常压下,将乙二胺加入到步骤2)制备的第二溶液中,充分搅拌得到第三溶液,其中,乙二胺与乙二醇的体积比为0.05~0.35∶1;3) Then, under normal temperature and pressure, ethylenediamine is added to the second solution prepared in step 2), and fully stirred to obtain a third solution, wherein the volume ratio of ethylenediamine to ethylene glycol is 0.05 to 0.35: 1; 4)接着,将步骤3)制备的第三溶液置于密闭的反应容器中,在200-250℃下,保温8~12小时,得到沉淀;4) Next, place the third solution prepared in step 3) in a closed reaction vessel, and keep it warm for 8-12 hours at 200-250° C. to obtain a precipitate; 5)最后,将上述步骤4)得到的沉淀用去离子水洗涤、干燥,即制得尖晶石型铁氧体纳米空心微球。5) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain spinel-type ferrite hollow nanospheres. 2.按照权利要求1所述的尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,所述M、M′和M″的盐选自含Co、Mn、Zn或Ni的二价盐,或者为三价铁盐。2. according to the preparation method of spinel type ferrite nano hollow microsphere according to claim 1, it is characterized in that, the salt of described M, M ' and M " is selected from containing Co, Mn, Zn or Ni Divalent salt, or ferric salt. 3.按照权利要求2所述的尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,所述的含Mn的二价盐选自Mn(NO3)2,MnCl2,MnSO4,Mn(CH3COO)2及其混合物。3. according to the preparation method of spinel type ferrite nano hollow microsphere according to claim 2, it is characterized in that, described divalent salt containing Mn is selected from Mn(NO 3 ) 2 , MnCl 2 , MnSO 4 , Mn(CH 3 COO) 2 and mixtures thereof. 4.按照权利要求2所述的尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,所述的含Zn的二价盐选自Zn(NO3)2,ZnCl2,ZnSO4,Zn(CH3COO)2及其混合物。4. according to the preparation method of spinel type ferrite nano hollow microsphere according to claim 2, it is characterized in that, described divalent salt containing Zn is selected from Zn(NO 3 ) 2 , ZnCl 2 , ZnSO 4 , Zn(CH 3 COO) 2 and mixtures thereof. 5.按照权利要求2所述的尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,所述的含Co的二价盐选自Co(NO3)2,CoCl2,CoSO4,Co(CH3COO)2及其混合物。5. according to the preparation method of spinel type ferrite nano hollow microsphere according to claim 2, it is characterized in that, described divalent salt containing Co is selected from Co(NO 3 ) 2 , CoCl 2 , CoSO 4 , Co(CH 3 COO) 2 and mixtures thereof. 6.按照权利要求2所述的尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,所述的含Ni的二价盐选自Ni(NO3)2,NiCl2,NiSO4,Ni(CH3COO)2及其混合物。6. according to the preparation method of spinel type ferrite nano hollow microsphere according to claim 2, it is characterized in that, described divalent salt containing Ni is selected from Ni(NO 3 ) 2 , NiCl 2 , NiSO 4 , Ni(CH 3 COO) 2 and mixtures thereof. 7.按照权利要求1或2所述的尖晶石型铁氧体纳米空心微球的制备方法,其特征在于,所述三价铁盐选自FeCl3,Fe(NO3)3,Fe2(SO4)3及其混合物。7. according to the preparation method of spinel type ferrite nano hollow microsphere described in claim 1 or 2, it is characterized in that, described ferric salt is selected from FeCl 3 , Fe(NO 3 ) 3 , Fe 2 (SO 4 ) 3 and mixtures thereof.
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