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

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

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

field of invention

The invention relates to a preparation method of spinel type ferrite nano hollow microspheres.

Background technique

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.

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.

Contents of the invention

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.

The purpose of the present invention is achieved through the following technical solutions:

The invention provides a preparation method of spinel ferrite nano hollow microspheres, the method comprising the following steps:

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 ) 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) 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) 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) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain spinel-type ferrite hollow nanospheres.

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.

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.

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.

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.

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.

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.

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.

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. 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. 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. The cost of raw materials required by the preparation method provided by the invention is low;

4. The whole preparation process provided by the present invention is carried out under air conditions without nitrogen protection;

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. 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.

Description of drawings

Fig. 1 is the scanning electron microscope (SEM) photo of the iron ferric oxide nano hollow microspheres that embodiment 1 makes;

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 ;

Fig. 4 is the electron diffraction figure (ED) of the cobalt ferrite nano hollow microsphere that embodiment 2 makes;

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).

Detailed ways

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.

Example 1

This embodiment prepares monodisperse ferric oxide nano hollow microspheres, the steps and conditions are as follows:

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) 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) 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) 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) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain monodisperse iron ferric oxide hollow nanospheres.

The preparation of the first, second, and third solutions above is all carried out at normal temperature and pressure.

The 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 .

Example 2

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.

Example 3

This example prepares monodisperse CoFe ₂ O ₄ ferrite nano hollow microspheres, the steps and conditions are as follows:

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) 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) 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) 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) 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.

The preparation of the above-mentioned first, second and third solutions is all carried out at normal temperature and pressure.

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.

Example 4

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.

Example 5

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.

Example 6

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.

Example 7

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.

Example 8

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) 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) 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) 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) 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) 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.

The preparation of the above-mentioned first, second and third solutions is all carried out at normal temperature and pressure.

Example 9

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.

Example 10

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.

Example 11

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.

Example 12

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.

Example 13

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.

Example 14

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.

Example 15

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.

Example 16

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.

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.

Example 17

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) 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) 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) 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) 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) 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.

The preparation of the above-mentioned first, second and third solutions is all carried out at normal temperature and pressure.

Example 18

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.

Example 19

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.

Example 20

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.

Example 21

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.

Example 22

Co _0.4 Ni _0.4 Mn _0.2 Fe ₂ O ₄

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.

Example 23

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.

Example 24

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.

Example 25

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.

Example 26

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.

Example 27

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.

Example 28

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.

Example 29

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.

Example 30

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.

Example 31

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.

Example 32

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.

Example 33

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.

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. a preparation method of spinel type ferrite nano hollow microspheres, is characterized in that, comprises the steps: 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 ) 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) 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) 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) Finally, the precipitate obtained in the above step 4) is washed with deionized water and dried to obtain spinel-type ferrite hollow nanospheres. 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. 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. 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. 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. 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. 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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