CN101289314B - Preparation method of spinel type ferrite nano hollow microspheres - Google Patents
Preparation method of spinel type ferrite nano hollow microspheres Download PDFInfo
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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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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 27
- 239000011029 spinel Substances 0.000 title claims abstract description 27
- 239000004005 microsphere Substances 0.000 title abstract 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 17
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 12
- 150000002505 iron Chemical class 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 241000080590 Niso Species 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910003321 CoFe Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000011319 anticancer therapy Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000005308 ferrimagnetism Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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- Soft Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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
Invention field
The present invention relates to a kind of preparation method of spinel type ferrite nano-hollow microballoon.
Background technology
Spinel type ferrite is a kind of important soft magnetic materials, and it is widely used in electron device, information storage and nuclear magnetic resonance fields such as (MRI).Development along with technology it is found that, when scantling reached nanoscale, it usually can show character such as the electricity different with block materials, magnetic, light, thereby nano material has obtained people and pays close attention to more and more.In recent years, nano magnetic material is also increasingly extensive in the practical application of the aspects such as magnetic transmission of magnetic storage, superfluid, medicine.Ferrite not only is used as the target of sensing and imaging, and it also is widely used as the promoting agent of anticancer therapy.For example, medical college of Japan Kobe university adopts nanometer ferrite to treat liver cancer, and kidney has just obtained than ten-strike.This shows that nanometer ferrite has good prospects for application aspect biological medicine.Therefore, synthesizing new nanometer ferrite magneticsubstance and its performance studied the focus that becomes broad research.
Because special hollow structure, nanometer ferrite magnetic hollow microballoon are expected to the carrier as effective drug delivery.At present, template method is adopted in the preparation of inorganic hollow microballoon usually, be template promptly with nano silicon oxide and polymer emulsion microballoon, by layer upon layer electrostatic self-assembly method, sol-gel method, sluggish precipitation etc., inorganics is coated on the template, remove template by pyrolysis or dissolving then, thereby obtain corresponding inorganic hollow microballoon.Yet, adopt this kind method to face unfavorable factors such as cost height, preparation process be numerous and diverse usually, be difficult to a large amount of preparations and large-scale production.Because the special difficulty of preparation, the preparation research of mono-dispersed nano ferrimagnetism hollow ball is phoenix feathers and unicorn horns especially, as J.Colloid ﹠amp; Interface Sci.2005,281,432 (Journal of Colloid and InterfaceScience, 281 volumes, 432 pages, 2005), Chem.Phys.Lett.2006,422,294 (Chemistry PhysicsLetters, 422 volumes, 294 pages, 2006) and J.Am.Chem.Soc.2006,128,8382 (Journal ofAmerican Chemistry Society, 128 volumes, 8382 pages, 2006) reported that respectively employing template and solvent-thermal method have prepared Z 250 and serial ferrite segmented copolymer tiny balloon, wherein the preparation of ferrite segmented copolymer tiny balloon is the iron trichloride with 3.0mmol, the Manganous chloride tetrahydrate of 1.5mmol or cobalt, and polyoxyethylene-polyoxytrimethylene of 43.6mmol sodium-acetate and 0.525mmol-polyethylene oxide block copolymer (PEO-PPO-PEO) is dissolved in the 35ml ethylene glycol solution, fully stir, change reactor over to, and be incubated 4 hours after centrifugal at 200 ℃, alcohol is washed, drying gets ferrite (Mn
1-xFe
2+xO
4The heterogeneous hollow micron ball of)/segmented copolymer.But the product that makes mostly is polycrystalline structure and has deficiencies such as surface irregularity, distribution of sizes is inhomogeneous, cavity is irregular.
Summary of the invention
The objective of the invention is to overcome defective such as the product surface that prior art for preparing spinel type ferrite tiny balloon obtains is coarse, distribution of sizes is inhomogeneous, cavity is irregular, is the preparation method of the spinel type ferrite nano-hollow microballoon of nano-scale, even particle size distribution thereby a kind of particle diameter is provided.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of preparation method of spinel type ferrite nano-hollow microballoon, this method comprises the steps:
1) at normal temperatures and pressures, trivalent iron salt is added in the ethylene glycol solution, fully stir and form first solution, wherein, the concentration of trivalent iron salt is 0.05～0.4mol/l;
2) according to the spinel type ferrite formula M
xM '
yM "
(1-x-y)Fe
2O
4In the salt of metal ions M, M ' and M " stoichiometric ratio take by weighing respectively contain M, M ' and M ", and at normal temperatures and pressures it is dissolved in first solution of step 1) preparation, fully stir and form second solution, wherein, described metal ions M, M ' and M " be selected from the divalent ion of Mn, Zn, Co and Ni and the trivalent ion of Fe respectively, and 0＜x≤1; 0≤y＜1, x+y≤1;
3) then, at normal temperatures and pressures, quadrol is joined step 2) in second solution of preparation, fully stir and obtain the 3rd solution, wherein, the volume ratio of quadrol and ethylene glycol is 0.05～0.35: 1;
4) then, the 3rd solution that step 3) is prepared places airtight reaction vessel, under 200-250 ℃, is incubated 8～12 hours, obtains precipitation;
5) last, with above-mentioned steps 4) the precipitate with deionized water washing, the drying that obtain, promptly make spinel type ferrite nano-hollow microballoon.
In one embodiment of the invention, described M, M ' and M " salt be preferably the divalent salts that contains Co, Mn, Zn or Ni, perhaps be trivalent iron salt.
In another embodiment of the invention, the divalent salts of the described Mn of containing is preferably Mn (NO
3)
2, MnCl
2, MnSO
4, Mn (CH
3COO)
2And composition thereof.
In yet another embodiment of the present invention, the divalent salts of the described Zn of containing is preferably Zn (NO
3)
2, ZnCl
2, ZnSO
4, Zn (CH
3COO)
2And composition thereof.
In another embodiment of the present invention, the divalent salts of the described Co of containing is preferably Co (NO
3)
2, CoCl
2, CoSO
4, Co (CH
3COO)
2And composition thereof.
In another embodiment of the present invention, the divalent salts of the described Ni of containing is preferably Ni (NO
3)
2, NiCl
2, NiSO
4, Ni (CH
3COO)
2And composition thereof.
In another embodiment of the present invention, described trivalent iron salt is preferably FeCl
3, Fe (NO
3)
3, Fe
2(SO
4)
3And composition thereof.
By the spinel type ferrite nano-hollow microballoon that preparation method provided by the invention obtains, its size is at 200～300nm, and wall thickness is at 20～40nm.
Compared with prior art, the preparation method of spinel type ferrite nano-hollow microballoon provided by the invention has following advantage:
1, the spinel type ferrite nano-hollow microballoon good dispersity for preparing of method provided by the invention, size is even, and size is at 200～300nm, and wall thickness is at 20～40nm;
2, the spinel type ferrite nano-hollow microballoon regular crystal forms for preparing of method provided by the invention is the pure monocrystalline spinel type ferrite of homogeneous phase;
3, the required material cost of preparation method provided by the invention is cheap;
4, whole process of preparation provided by the invention is all carried out under air conditions, need not nitrogen protection;
5, among the preparation method provided by the invention, ferritic preparation solvent heat treatment under lesser temps (200～250 ℃) can obtain homogeneous spinel type ferrite tiny balloon;
6, preparation method's technology provided by the invention is simple, can prepare in a large number, is suitable for large-scale production.
Description of drawings
Scanning electron microscope (SEM) photo of the ferriferrous oxide nano tiny balloon that Fig. 1 makes for embodiment 1;
The electronic energy spectrum (EDX) of the ferriferrous oxide nano tiny balloon that Fig. 2 makes for embodiment 1; Transmission electron microscope (TEM) photo of the vectolite nano-hollow microballoon that Fig. 3 makes for embodiment 2;
The electron-diffraction diagram (ED) of the vectolite nano-hollow microballoon that Fig. 4 makes for embodiment 2;
The MnFe that Fig. 5 makes for embodiment 3,5,11 and 15
2O
4, CoFe
2O
4, Mn
0.5Zn
0.5Fe
2O
4, Co
0.5Ni
0.5Fe
2O
4The nano-hollow microballoon X-ray diffraction spectrogram (XRD).
Embodiment
Further set forth the present invention below in conjunction with drawings and Examples, be not used in but these embodiment only limit to the present invention is described and limit the scope of the invention.Protection scope of the present invention is as the criterion with appending claims.
The single ferriferrous oxide nano tiny balloon that disperses of present embodiment preparation, step and condition are as follows:
1) with an amount of FeCl
3Be dissolved in 40ml ethylene glycol, fully stir and form FeCl
3Concentration is the settled solution of 0.4mol/l, i.e. first solution;
2) with Fe (NO
3)
3According to mol ratio Fe (NO
3)
3: FeCl
3=1:2 joins in first solution, fully stirs to form second solution;
3) quadrol dropwise is added drop-wise in second solution, the volume ratio of its add-on and ethylene glycol is 0.2:1, fully stirs to form i.e. the 3rd solution;
4) the 3rd solution with above-mentioned gained forwards in the airtight reaction vessel, under 200 ℃ condition, is incubated 8 hours, obtains precipitation;
5) last, with above-mentioned steps 4) the precipitate with deionized water washing, the drying that obtain, promptly make monodispersed ferriferrous oxide nano tiny balloon.
The preparation of above-mentioned first, second and the 3rd solution is all carried out at normal temperatures and pressures.
The electron microscope scanning photo of the ferriferrous oxide nano tiny balloon of present embodiment preparation and electronic energy spectrum are respectively as depicted in figs. 1 and 2, the sample surfaces that as can be seen from Figure 1 makes is comparatively smooth, and good dispersity, particle diameter is even, size is at 200～300nm, wall thickness is at 20～40nm, and the broken spheroid of part presents semisphere and bowl-type, proves that the sample that makes has hollow structure; The sample that as can be seen from Figure 2 makes only contains Fe and two kinds of elements of O (wherein Au is conduction needs, the gold that is sprayed during sample preparation), and according to the electronic spectrum data as can be known, element number Fe/O～3/4, it is Fe that preliminary proof makes sample
3O
4
Use iron nitrate (Fe (NO except step 1) in the present embodiment
3)
3) or ferric sulfate (Fe
2(SO
4)
3) alternative iron(ic) chloride (FeCl
3) outside, other steps are all identical with embodiment 1 with condition, can obtain monocrystalline, single ferriferrous oxide nano tiny balloon that disperses equally.
The single CoFe that disperses of present embodiment preparation
2O
4The ferrite nano tiny balloon, its step and condition are as follows:
1) with an amount of Fe
2(SO
4)
3Be dissolved in 40ml ethylene glycol, fully stir and form Fe
2(SO
4)
3Concentration is first solution of 0.05mol/l;
2) with Co (NO
3)
2According to stoichiometric ratio Co
2+: Fe
3+=1:2 joins in first solution, fully stirs to form second solution;
3) quadrol dropwise is added drop-wise in second solution, the volume ratio of its add-on and ethylene glycol is 0.35:1, fully stirs to form the 3rd solution;
4) the 3rd solution with above-mentioned gained forwards in the airtight reaction vessel, under 250 ℃ condition, is incubated 12 hours, obtains precipitation;
5) last, with above-mentioned steps 4) the precipitate with deionized water washing, the drying that obtain, promptly make monodispersed CoFe
2O
4The ferrite nano tiny balloon.
The preparation of above-mentioned first, second and the 3rd solution is all carried out at normal temperatures and pressures.
The CoFe of present embodiment preparation
2O
4The transmission electron microscope of ferrite nano tiny balloon (TEM) photo and electron-diffraction diagram (ED) are respectively as shown in Figure 3 and Figure 4, product edge that as can be seen from Figure 3 makes and centre portions have tangible contrast gradient, wherein edge color is darker, the centre portions color is more shallow, this shows that the sample that makes has hollow structure, good dispersity, and particle diameter is even, size is at 200～300nm, and wall thickness is at 20～40nm; As can be seen from Figure 4 sample presents typical single crystal diffraction decorative pattern, shows that the sample that makes has single crystal characteristics.
Remove in the step 1) in the present embodiment and increase Fe
2(SO
4)
3Concentration to 0.4mol/l, simultaneously quadrol in the step 3) and ethylene glycol volume ratio are reduced to outside the 0.05:1, other conditions are identical with embodiment 3 with step, can obtain single CoFe of dispersion equally
2O
4The ferrite nano tiny balloon.
Remove step 2 in the present embodiment) use MnCl
2Substitute Co (NO
3)
2Outward, other steps are identical with embodiment 3 with condition, can obtain monocrystalline, monodispersed MnFe
2O
4The ferrite nano tiny balloon.
Remove step 2 in the present embodiment) use ZnSO
4Substitute Co (NO
3)
2Outward, other steps are identical with embodiment 3 with condition, can obtain monocrystalline, monodispersed ZnFe
2O
4The ferrite nano tiny balloon.
Embodiment 7
Remove step 2 in the present embodiment) use Ni (CH
3COO)
2Substitute Co (NO
3)
2Outward, other steps are identical with embodiment 3 with condition, can obtain monocrystalline, monodispersed NiFe
2O
4The ferrite nano tiny balloon.
Embodiment 8
The single Mn that disperses of present embodiment preparation
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon, its step and condition are as follows:
1) with an amount of Fe (NO
3)
3Be dissolved in 40ml ethylene glycol, fully stir and form Fe (NO
3)
3Concentration is first solution of 0.2mol/l;
2) with Mn (NO
3)
2And ZnSO
4According to stoichiometric ratio Mn
2+: Zn2
+: Fe
3+=0.5:0.5:2; Join in first solution, fully stir and form second solution;
3) quadrol dropwise is added drop-wise in second solution, the volume ratio of its add-on and ethylene glycol is 0.1:1, fully stirs to form the 3rd solution;
4) the 3rd solution with above-mentioned gained forwards in the airtight reaction vessel, under 250 ℃ condition, is incubated 10 hours, obtains precipitation;
5) last, with above-mentioned steps 4) the precipitate with deionized water washing, the drying that obtain, promptly make monodispersed Mn
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon.
The preparation of above-mentioned first, second and the 3rd solution is all carried out at normal temperatures and pressures.
Embodiment 9
Remove step 1) in the present embodiment and increase Fe (NO
3)
3Concentration to 0.4mol/l, simultaneously quadrol in the step 3) and ethylene glycol volume ratio are reduced to outside the 0.05:1, other steps are identical with embodiment 8 with condition, can obtain Mn equally
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon.
Remove step 1) in the present embodiment and reduce Fe (NO
3)
3Concentration to 0.05mol/l, simultaneously quadrol in the step 3) and ethylene glycol volume ratio are increased to outside the 0.35:1, other steps are identical with embodiment 8 with condition, can obtain Mn equally
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon.
Embodiment 11
Remove step 2 in the present embodiment) the middle Mn (NO that adds
3)
2And ZnSO
4Respectively by NiCl
2And CoSO
4Outside substituting, other conditions are identical with embodiment 8 with step, equally also obtain Mn
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon.
Embodiment 12
Remove step 2 in the present embodiment) the middle Mn (NO that adds
3)
2And ZnSO
4Respectively by Co (NO
3)
2And ZnCl
2Outside substituting, other conditions are identical with embodiment 8 with step, equally also obtain Co
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon.
Embodiment 13
Remove step 2 in the present embodiment) the middle Mn (NO that adds
3)
2And ZnSO
4Respectively by MnSO
4And CoCl
2Outside substituting, other conditions are identical with embodiment 8 with step, equally also obtain Mn
0.5Co
0.5Fe
2O
4The ferrite nano tiny balloon.
Embodiment 14
Remove step 2 in the present embodiment) the middle Mn (NO that adds
3)
2And ZnSO
4Respectively by NiSO
4And Zn (NO
3)
2Outside substituting, other conditions are identical with embodiment 8 with step, equally also obtain Ni
0.5Zn
0.5Fe
2O
4The ferrite nano tiny balloon.
Embodiment 15
Remove step 2 in the present embodiment) the middle Mn (NO that adds
3)
2And ZnSO
4Respectively by Co (CH
3COO)
2And Ni (CH
3COO)
2Outside substituting, other conditions are identical with embodiment 8 with step, equally also obtain Co
0.5Ni
0.5Fe
2O
4The ferrite nano tiny balloon.
Embodiment 16
Remove step 2 in the present embodiment) the middle Mn (NO that adds
3)
2And NiSO
4Respectively by Mn (CH
3COO)
2And Ni (NO
3)
2Outside substituting, other conditions are identical with embodiment 8 with step, equally also obtain Mn
0.5Ni
0.5Fe
2O
4The ferrite nano tiny balloon.
Fig. 5 has provided embodiment 3,5,11,15 CoFe that make
2O
4, MnFe
2O
4, Mn
0.5Zn
0.5Fe
2O
4, Co
0.5Ni
0.5Fe
2O
4The nano-hollow microballoon X-ray diffraction spectrogram (XRD), the spinel type ferrite of the cubic structure of the sample pure phase that as can be seen from the figure makes, and the intensity of diffraction peak is higher, shows that the sample that makes has high degree of crystallization, crystalline form is comparatively complete.
Embodiment 17
The single Co that disperses of present embodiment preparation
0.4Mn
0.4Zn
0.2Fe
2O
4The ferrite nano tiny balloon, its step and condition are as follows:
1) with an amount of Fe
2(SO
4)
3Be dissolved in 40ml ethylene glycol, fully stir and form Fe
2(SO
4)
3Concentration is first solution of 0.4mol/l;
2) with Co (CH
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2According to stoichiometric ratio Co
2+: Mn
2+: Zn
2+: Fe
3+=0.4:0.4:0.2:2 joins in first solution, fully stirs to form second solution;
3) quadrol dropwise is added drop-wise in second solution, the volume ratio of its add-on and ethylene glycol is 0.3:1, fully stirs to form the 3rd solution;
4) the 3rd solution with above-mentioned gained forwards in the airtight reaction vessel, under 210 ℃ condition, is incubated 11 hours, obtains precipitation;
5) last, with above-mentioned steps 4) the precipitate with deionized water washing, the drying that obtain, promptly make monodispersed Co
0.4Mn
0.4Zn
0.2Fe
2O
4The ferrite nano tiny balloon.
The preparation of above-mentioned first, second and the 3rd solution is all carried out at normal temperatures and pressures.
Embodiment 18
Remove step 1) in the present embodiment and reduce Fe
2(SO
4)
3Concentration to 0.05mol/l, simultaneously quadrol in the step 3) and ethylene glycol volume ratio are reduced to outside the 0.05:1, other steps are identical with embodiment 17 with condition, can obtain Co equally
0.4Mn
0.4Zn
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 19
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by Ni (NO
3)
2, MnSO
4And ZnCl
2Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Ni
0.4Mn
0.4Zn
0.2Fe
2O
4The ferrite nano tiny balloon.
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by Co (NO
3)
2, NiSO
4And ZnCl
2Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Ni
0.4Zn
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 21
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by CoSO
4, ZnSO
4And MnSO
4Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Zn
0.4Mn
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 22
Co
0.4Ni
0.4Mn
0.2Fe
2O
4
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by CoCl
2, NiCl
2And Mn (NO
3)
2, substitute outside, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Ni
0.4Mn
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 23
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by Zn (NO
3)
2, Ni (CH
3COO)
2And MnSO
4Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Zn
0.4Ni
0.4Mn
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 24
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by MnSO
4, ZnCl
2And Co (NO
3)
2Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Mn
0.4Zn
0.4Co
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 25
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by MnSO
4, Ni (CH
3COO)
2And CoCl
2Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Mn
0.4Ni
0.4Co
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 26
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by Ni (NO
3)
2, ZnCl
2, and CoSO
4Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Ni
0.4Zn
0.4Co
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 27
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by Co (NO
3)
2, MnSO
4And NiCl
2Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Mn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 28
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by ZnCl
2, MnCl
2And Ni (CH
3COO)
2Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Zn
0.4Mn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon.
Embodiment 29
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2, Mn (CH
3COO)
2And Zn (CH
3COO)
2Respectively by Co (NO
3)
2, ZnCl
2And NiSO
4Outside substituting, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Zn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon.
Remove step 2 in the present embodiment) the middle Co (CH that adds
3COO)
2By Co (NO
3)
2And CoCl
2Mixture replacing outside, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Zn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon, wherein, Co (NO
3)
2And CoCl
2Can mix by arbitrary proportion, as long as keep the stoichiometric ratio of each metal ion in second solution still to satisfy Co
2+: Mn
2+: Zn
2+: Fe
3+=0.4:0.4:0.2:2 gets final product.
Embodiment 31
Remove step 2 in the present embodiment) the middle Mn (CH that adds
3COO)
2By MnSO
4, Mn (NO
3)
2And MnCl
2Mixture replacing outside, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Zn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon, wherein, MnSO
4, Mn (NO
3)
2And MnCl
2Can mix by arbitrary proportion, as long as keep the stoichiometric ratio of each metal ion in second solution still to satisfy Co
2+: Mn
2+: Zn
2+: Fe
3+=0.4:0.4:0.2:2 gets final product.
Embodiment 32
Remove step 2 in the present embodiment) the middle Zn (CH that adds
3COO)
2By ZnSO
4, Zn (CH
3COO)
2, Zn (NO
3)
2And ZnCl
2Mixture replacing outside, other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Zn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon, wherein, ZnSO
4, Zn (CH
3COO)
2, Zn (NO
3)
2And ZnCl
2Can mix by arbitrary proportion, as long as keep the stoichiometric ratio of each metal ion in second solution still to satisfy Co
2+: Mn
2+: Zn
2+: Fe
3+=0.4:0.4:0.2:2 gets final product.
Embodiment 33
Remove step 1) in the present embodiment and use FeCl
3And Fe (NO
3)
3Mixture replacing Fe
2(SO
4)
3Outward, other other conditions are identical with embodiment 17 with step, equally also obtain Co
0.4Zn
0.4Ni
0.2Fe
2O
4The ferrite nano tiny balloon, wherein, FeCl
3And Fe (NO
3)
3Proportioning can be arbitrarily, as long as Fe in first solution that guarantees finally to obtain
3+Concentration and embodiment 17 in Fe in first solution
3+Identical the getting final product of concentration.
Below in conjunction with embodiment the present invention has been done to specify, all variants, modification, alternative and the equivalent that it will be appreciated by those skilled in the art that embodiment of the present invention are all within the scope of the present invention.
Claims (7)
1. the preparation method of a spinel type ferrite nano-hollow microballoon is characterized in that, comprises the steps:
1) at normal temperatures and pressures, trivalent iron salt is added in the ethylene glycol solution, fully stir and form first solution, wherein, the concentration of trivalent iron salt is 0.05～0.4mol/l;
2) according to the spinel type ferrite formula M
xM '
yM "
(1-x-y)Fe
2O
4In the salt of metal ions M, M ' and M " stoichiometric ratio take by weighing respectively contain M, M ' and M ", and at normal temperatures and pressures it is dissolved in first solution of step 1) preparation, fully stir and form second solution, wherein, described metal ions M, M ' and M " be selected from the divalent ion of Mn, Zn, Co and Ni and the trivalent ion of Fe respectively, and 0＜x≤1; 0≤y＜1, x+y≤1;
3) then, at normal temperatures and pressures, quadrol is joined step 2) in second solution of preparation, fully stir and obtain the 3rd solution, wherein, the volume ratio of quadrol and ethylene glycol is 0.05～0.35: 1;
4) then, the 3rd solution that step 3) is prepared places airtight reaction vessel, under 200-250 ℃, is incubated 8～12 hours, obtains precipitation;
5) last, with above-mentioned steps 4) the precipitate with deionized water washing, the drying that obtain, promptly make spinel type ferrite nano-hollow microballoon.
2. according to the preparation method of the described spinel type ferrite nano-hollow of claim 1 microballoon, it is characterized in that described M, M ' and M " salt be selected from the divalent salts that contains Co, Mn, Zn or Ni, perhaps be trivalent iron salt.
3. according to the preparation method of the described spinel type ferrite nano-hollow of claim 2 microballoon, it is characterized in that the divalent salts of the described Mn of containing is selected from Mn (NO
3)
2, MnCl
2, MnSO
4, Mn (CH
3COO)
2And composition thereof.
4. according to the preparation method of the described spinel type ferrite nano-hollow of claim 2 microballoon, it is characterized in that the divalent salts of the described Zn of containing is selected from Zn (NO
3)
2, ZnCl
2, ZnSO
4, Zn (CH
3COO)
2And composition thereof.
5. according to the preparation method of the described spinel type ferrite nano-hollow of claim 2 microballoon, it is characterized in that the divalent salts of the described Co of containing is selected from Co (NO
3)
2, CoCl
2, CoSO
4, Co (CH
3COO)
2And composition thereof.
6. according to the preparation method of the described spinel type ferrite nano-hollow of claim 2 microballoon, it is characterized in that the divalent salts of the described Ni of containing is selected from Ni (NO
3)
2, NiCl
2, NiSO
4, Ni (CH
3COO)
2And composition thereof.
7. according to the preparation method of claim 1 or 2 described spinel type ferrite nano-hollow microballoons, it is characterized in that described trivalent iron salt is selected from FeCl
3, Fe (NO
3)
3, Fe
2(SO
4)
3And composition thereof.
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| WO2013029200A1 (en) * | 2011-08-29 | 2013-03-07 | 山西省电力公司 | Method for preparing hollow ni-zn ferrite microsphere |
| CN102408231B (en) * | 2011-08-29 | 2013-06-19 | 山西省电力公司晋城供电分公司 | Preparation method of hollow Ni-Zn ferrite microsphere |
| CN102502867A (en) * | 2011-10-12 | 2012-06-20 | 上海第二工业大学 | Preparation method of F-doped gamma-ferric oxide hollow microspheres with adjustable bandwidth |
| CN102963938B (en) * | 2012-11-20 | 2014-11-05 | 上海第二工业大学 | Spinel ferrite/CNx nanocomposite and preparation method thereof |
| CN103101980A (en) * | 2013-03-06 | 2013-05-15 | 鲁东大学 | Preparation method of multiaperture ferrite |
| CN104569080A (en) * | 2015-01-30 | 2015-04-29 | 吉林大学 | Acetone gas sensor based on hollow spherical ZnFe2O4 nano material and preparation method thereof |
| CN105692714B (en) * | 2016-01-24 | 2017-06-27 | 上海应用技术学院 | A kind of hydrothermal synthesis method of the iron-based spinelle with high density Lacking oxygen |
| CN106229154B (en) * | 2016-08-23 | 2018-08-31 | 宁波中车新能源科技有限公司 | A kind of ultracapacitor aoxidizing combination electrode material based on nanometer ferromanganese |
| CN106298256B (en) * | 2016-08-23 | 2019-03-08 | 宁波中车新能源科技有限公司 | A kind of nanostructured manganese iron oxidation combination electrode material and preparation method thereof for supercapacitor |
| CN106582602B (en) * | 2016-12-28 | 2020-03-17 | 厦门大学 | Efficient synthesis method of series spinel nano-structure materials |
| CN108101531B (en) * | 2017-12-15 | 2020-09-22 | 华南理工大学 | Composite spinel material with high infrared emissivity and preparation method thereof |
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