CN102502879A - Fe3O4 nano-microsphere and preparation method thereof - Google Patents

Fe3O4 nano-microsphere and preparation method thereof Download PDF

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Publication number
CN102502879A
CN102502879A CN2011103405171A CN201110340517A CN102502879A CN 102502879 A CN102502879 A CN 102502879A CN 2011103405171 A CN2011103405171 A CN 2011103405171A CN 201110340517 A CN201110340517 A CN 201110340517A CN 102502879 A CN102502879 A CN 102502879A
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nano microsphere
preparation
microsphere
nano
fecl
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娄蕾
郁可
朱建中
张正犁
王依婷
朱自强
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East China Normal University
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East China Normal University
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Abstract

The invention discloses a Fe3O4 nano-microsphere preparation method, which includes: adding NaOH into raw materials including FeCl2 and FeCl3 to adjust pH, preparing Fe3O4 under heating reaction, and using polyethylenimine as cationic surfactant to modify surface of the Fe3O4 so as to obtain the Fe3O4 nano-microsphere. The Fe3O4 nano-microsphere preparation method is simple in synthesis process, low in cost, quick and safe in preparation and easy in implementation of industrial production, and production equipment is simple. The Fe3O4 nano-microsphere prepared by the method is excellent in magnetic performance and high in dispersity.

Description

A kind of Fe 3O 4Nano microsphere and preparation method thereof
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of Fe 3O 4Nano microsphere and preparation method thereof.
Background technology
The nano-magnetic ferriferrous oxide material is used very extensive.Characteristics such as its tool grain diameter is little, specific surface area is very high, magnetosensitive are used the prospect that light is arranged in fields such as bioseparation, targeted drug, tumour magnetic thermotherapy and immunodetection.Because the special physics and chemistry of nano ferriferrous oxide is learned character, make its in practical application more and more widely, and its preparation method and Study on Properties have also obtained deep progress.Simultaneously; Because magnetic such as ferriferrous oxide nano-particle have very big specific surface area; Magnetic idol interpolar attracts each other and all is prone to cause the generation of agglomeration, so how to prepare particle diameter is little, the ferriferrous oxide nano-particle of good dispersivity has become the research focus that receives much attention now.
The present invention has overcome that cost of the prior art is higher, the preparation process is complicated and defective such as kind wayward, product is limited, and a kind of Fe is provided 3O 4The preparation method of Nano microsphere has the wide beneficial effect of kind scope that cost is low, prepare process simple controllable, product.Fe of the present invention 3O 4Adopted the method for self-assembly in the preparation of Nano microsphere.Through at electronegative Fe 3O 4The surface superscribes the polymine of one deck positively charged, reaches control and reunites, and keeps the purpose of particles dispersed.Wherein, Fe 3O 4Material is of a size of 40nm – 60 nm, and the polyethyleneimine: amine layer thichness is about 1 nm, and the tensio-active agent cationic polyethyleneimine is to Fe 3O 4Modification is carried out on the surface.The present invention has confirmed nanometer Fe through TEM test and magnetic test 3O 4The excellent properties of microballoon is with its application in every respect of further promotion.
Summary of the invention
The present invention proposes a kind of Fe 3O 4The preparation method of Nano microsphere may further comprise the steps successively:
A) with FeCl 2And FeCl 3Mix in the adding deionized water, obtain solution;
B) at N 2Under the protection environment, said solution is heated to 60 ℃～100 ℃, regulates pH to 11, vigorous stirring 2h obtains Fe 3O 4
C) add the 0.1g/mL polymine, obtain said Fe through modification 3O 4Nano microsphere.
Fe of the present invention 3O 4The preparation method of Nano microsphere also can further may further comprise the steps:
D) the said Fe that step c is obtained 3O 4Nano microsphere cleans 5～20 times repeatedly;
E) with said Fe 3O 4Nano microsphere is soluble in water, obtains Fe 3O 4Nano microsphere solution.
Wherein, among the said step a, FeCl 2And FeCl 3Mixed in molar ratio with 1:2.
Wherein, among the said step b, it is to carry out through dropwise adding 1 mol/L NaOH solution that the pH value is regulated.
Wherein, the temperature among the said step b is preferably 70 ℃～80 ℃.
Wherein, in the said steps d, the said Fe of the method for cleaning for using magnet that step c is obtained 3O 4Nano microsphere is separated, and is dissolved in the deionized water through the UW effect again, cleans.
The said Fe that method produced according to the present invention obtains 3O 4Nano microsphere, it comprises Fe 3O 4Face-centred cubic structure be wrapped in said Fe 3O 4The lip-deep polymine layer of face-centred cubic structure.
Wherein, said Fe 3O 4The Nano microsphere particle diameter is 40nm – 60 nm, and said polyethyleneimine: amine layer thichness is 0.5～2 nm.
Fe of the present invention 3O 4Nano microsphere has good dispersiveness and magnetic behavior, at room temperature, no hysteresis, no remanent magnetism, no coercive field, saturation magnetization is 60-80 emu/g.Fe of the present invention 3O 4Nano microsphere magnetic is strong, uses common magnet promptly separable, shows the superparamagnetism performance at normal temperatures.Good dispersivity, soluble in water can the dispersion.
The invention provides a kind of preparation Fe 3O 4The method of Nano microsphere.This method is a starting raw material with high iron(ic)chloride, iron protochloride and sodium hydroxide, preparation Fe 3O 4, and adopt the cats product polymine to Fe 3O 4Carry out surface-treated, prepare the Fe of good dispersibility 3O 4Nano microsphere.Excellent for the preparation magnetic performance, good dispersivity and synthesis technique and required production unit are simple, and cost is low, prepare fast and safety, are easy to realize the Fe of suitability for industrialized production 3O 4Nano microsphere.
Fe of the present invention 3O 4Nano microsphere has adopted the method for self-assembly in the preparation.Through at electronegative Fe 3O 4The surface superscribes the polymine of one deck positively charged, reaches control and reunites, and keeps the purpose of particles dispersed.
Fe according to the invention 3O 4Nano microsphere has good dispersiveness and magnetic behavior, at room temperature, does not find hysteresis, no remanent magnetism, no coercive field.These character make Fe 3O 4Nano microsphere can be separated by permanent magnet rapidly, can when no magnetic field, be dissolved in the solution apace again.The X-ray diffraction test shows, the Fe that the present invention is prepared 3O 4Nano microsphere is a face-centred cubic structure.Crystallinity is good, does not find other impurity.Simultaneously, through the temperature of reaction among the control preparation method of the present invention, can prepare the Fe of 40-60nm different-grain diameter size 3O 4Nano microsphere.
The present invention has synthesized Fe through the control to some parameters in the self-assembly method 3O 4Nano microsphere.With respect to the similar nano composite structure of the synthetic of former report, the present invention has following characteristics: preparing method's cost of the present invention is low, and preparation is quick, safety, and is low for equipment requirements; The Fe that the present invention is prepared 3O 4The Nano microsphere good dispersivity, soluble in water can the dispersion; The Fe that the present invention is prepared 3O 4Nano microsphere magnetic is strong, uses common magnet promptly separable, shows the superparamagnetism performance at normal temperatures; The present invention is easy to through control reaction temperature, the Fe of preparation different size particle diameter 3O 4Nano microsphere; The inventive method is simple, and cost is low, and good reproducibility can be used for mass preparation.
Description of drawings
Fig. 1 is embodiment 1 prepared Fe 3O 4The X-ray diffractogram of Nano microsphere.
Fig. 2 is embodiment 1 prepared Fe 3O 4The TEM photo of Nano microsphere.
Fig. 3 is embodiment 2 prepared Fe 3O 4The TEM photo of Nano microsphere.
Fig. 4 is embodiment 1 prepared Fe 3O 4The hysteresis curve of Nano microsphere.
Embodiment
In conjunction with following specific embodiment and accompanying drawing, the present invention is done further detailed description, protection content of the present invention is not limited to following examples.Under spirit that does not deviate from inventive concept and scope, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection domain with the appending claims.
The present invention prepares the Fe of different size 3O 4The method of Nano microsphere may further comprise the steps successively:
A) with FeCl 2And FeCl 3Ratio with mol ratio 1:2 is dissolved in the deionized water, obtains solution;
B) at N 2Under the protection environment, the solution that obtains among the step a is heated to 60 ℃～100 ℃, 1 mol/L NaOH solution is dropwise added in the mixing solutions of step a, regulate pH value to 11, vigorous stirring 2h obtains not having the Fe that polymkeric substance wraps up 3O 4
C) the 0.1g/mL polymine is added, obtain Fe of the present invention through modification 3O 4Nano microsphere;
D) Fe that uses magnet that step c is obtained 3O 4Nano microsphere is separated, and under the UW effect, is dissolved in the deionized water again, cleans so repeatedly 5～20 times, to remove unnecessary reactive ion.
E) with Fe 3O 4Nano microsphere is dissolved in the deionized water, obtains Fe 3O 4Nano microsphere solution.
Embodiment 1
Fe 3O 4The preparation of Nano microsphere may further comprise the steps:
(1) with FeCl 2And FeCl 3Ratio with mol ratio 1:2 is dissolved in the deionized water;
(2) at N 2Under the protection environment, the solution that step 1 is obtained is heated to 75 ℃, in the mixing solutions that 1 mol/L NaOH solution is dropwise added, regulates pH value to 11, and vigorous stirring 2h obtains not having the Fe that polymkeric substance wraps up 3O 4
(3) the 0.1g/mL polymine is added, obtain Fe of the present invention through modification 3O 4Nano microsphere;
(4) Fe that uses magnet that step 3 is obtained 3O 4Nano microsphere is separated, and under the UW effect, is dissolved in the deionized water again, cleans so repeatedly 5～20 times.
(5) with the Fe that cleans 3O 4Nano microsphere is dissolved in the deionized water, obtains Fe 3O 4Nano microsphere solution.
As shown in Figure 1, X-ray diffraction test shows, the Fe that the present invention is prepared 3O 4Nano microsphere is a face-centred cubic structure, and crystallinity is good, does not find other impurity.As shown in Figure 2, Fe 3O 4Nano microsphere presents good dispersiveness, and particle diameter is 45nm – 55 nm, resulting Fe 3O 4Nano microsphere comprises Fe 3O 4Face-centred cubic structure be wrapped in its lip-deep polymine layer.Wherein, Fe 3O 4The Nano microsphere particle diameter is 45nm – 55 nm, and the polyethyleneimine: amine layer thichness is 0.5-2nm.As shown in Figure 4, Fe 3O 4Nano microsphere has good magnetic behavior, at room temperature, does not find hysteresis, no remanent magnetism, and no coercive field, saturation magnetization is 60-80 emu/g.These character make Fe of the present invention 3O 4Nano microsphere can be separated by permanent magnet rapidly, can when no magnetic field, be dissolved in the solution apace again.
Embodiment 2
The temperature of step 2 is 90 ℃, and all the other are identical with embodiment 1.
As shown in Figure 3, Fe 3O 4Nano microsphere presents good dispersiveness, and particle diameter is 50 nm –, 60 nm, resulting Fe 3O 4Nano microsphere comprises Fe 3O 4Face-centred cubic structure and the parcel its lip-deep polymine layer.Wherein, Fe 3O 4The Nano microsphere particle diameter is 50 nm –, 60 nm, and the polyethyleneimine: amine layer thichness is 0.5-2nm.
Comparing embodiment 1 and embodiment 2 can be found Fe 3O 4The particle size of Nano microsphere is relevant with the temperature of reaction of setting, and when temperature raise, it is big that particle radius also becomes.The preferred temperature of reaction of preparation method of the present invention is 70 ℃～80 ℃, can prepare to have good dispersibility, and particle diameter is even, and size is about 45-55 nm, and there is the Fe of the polymine modification about 1nm on the surface 3O 4Nano microsphere, saturation magnetization are 60-80emu/g.

Claims (9)

1. Fe 3O 4The preparation method of Nano microsphere is characterized in that, may further comprise the steps successively:
A) with FeCl 2And FeCl 3Mix in the adding deionized water, obtain solution;
B) at N 2Down, said solution is heated to 60 ℃～100 ℃, regulates pH to 11, vigorous stirring 2h obtains Fe 3O 4
C) add the 0.1g/mL polymine, obtain said Fe through modification 3O 4Nano microsphere.
2. Fe according to claim 1 3O 4The preparation method of Nano microsphere is characterized in that, further may further comprise the steps:
D) the said Fe that step c is obtained 3O 4Nano microsphere cleans 5～20 times repeatedly;
E) with said Fe 3O 4Nano microsphere is dissolved in the deionized water, obtains Fe 3O 4Nano microsphere solution.
3. Fe according to claim 1 3O 4The preparation method of Nano microsphere is characterized in that, among the said step a, and FeCl 2And FeCl 3Mixed in molar ratio with 1:2.
4. Fe according to claim 1 3O 4The preparation method of Nano microsphere is characterized in that, among the said step b, it is to carry out through dropwise adding 1 mol/L NaOH solution that the pH value is regulated.
5. Fe according to claim 1 3O 4The preparation method of Nano microsphere is characterized in that, the temperature among the said step b is preferably 70 ℃～80 ℃.
6. Fe according to claim 2 3O 4The preparation method of Nano microsphere is characterized in that, in the said steps d, and the said Fe of the method for cleaning for using magnet that step c is obtained 3O 4Nano microsphere is separated, and is dissolved in the deionized water through the UW effect again, cleans.
7. the said Fe that preparation method according to claim 1 obtains 3O 4Nano microsphere is characterized in that, said Fe 3O 4Nano microsphere comprises Fe 3O 4Face-centred cubic structure be wrapped in said Fe 3O 4The lip-deep polymine layer of face-centred cubic structure.
8. Fe according to claim 7 3O 4Nano microsphere is characterized in that, said Fe 3O 4The Nano microsphere particle diameter is 40nm – 60 nm, and said polyethyleneimine: amine layer thichness is 0.5-2 nm.
9. Fe according to claim 7 3O 4Nano microsphere is characterized in that, said Fe 3O 4Nano microsphere grain saturation magnetization is 60-80 emu/g.
CN2011103405171A 2011-11-02 2011-11-02 Fe3O4 nano-microsphere and preparation method thereof Pending CN102502879A (en)

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CN103112904A (en) * 2013-02-25 2013-05-22 哈尔滨理工大学 Preparation method of nano Fe3O4 powder for preparation of nano dielectric medium through compounding with polyethylene
CN105645477A (en) * 2016-03-21 2016-06-08 黄山学院 Preparation method of ferroferric oxide
CN109781702A (en) * 2019-01-18 2019-05-21 中国人民解放军军事科学院军事医学研究院 A kind of detection method of magnetic microsphere and preparation method thereof and microorganism
CN111330555A (en) * 2020-03-13 2020-06-26 天津迪沃特生物电子科技有限公司 Magnetic core-shell mesoporous silica gel material and preparation method and application thereof
CN112978803A (en) * 2021-02-23 2021-06-18 四川大学 Preparation method of water-soluble superparamagnetic ferroferric oxide microspheres with positively charged surfaces
WO2022146349A1 (en) * 2020-12-30 2022-07-07 T.C. Erci̇yes Üni̇versi̇tesi̇ A polymer nanocomposite adsorbent and production method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103112904A (en) * 2013-02-25 2013-05-22 哈尔滨理工大学 Preparation method of nano Fe3O4 powder for preparation of nano dielectric medium through compounding with polyethylene
CN103112904B (en) * 2013-02-25 2014-12-17 哈尔滨理工大学 Preparation method of nano Fe3O4 powder for preparation of nano dielectric medium through compounding with polyethylene
CN105645477A (en) * 2016-03-21 2016-06-08 黄山学院 Preparation method of ferroferric oxide
CN109781702A (en) * 2019-01-18 2019-05-21 中国人民解放军军事科学院军事医学研究院 A kind of detection method of magnetic microsphere and preparation method thereof and microorganism
CN111330555A (en) * 2020-03-13 2020-06-26 天津迪沃特生物电子科技有限公司 Magnetic core-shell mesoporous silica gel material and preparation method and application thereof
WO2022146349A1 (en) * 2020-12-30 2022-07-07 T.C. Erci̇yes Üni̇versi̇tesi̇ A polymer nanocomposite adsorbent and production method thereof
CN112978803A (en) * 2021-02-23 2021-06-18 四川大学 Preparation method of water-soluble superparamagnetic ferroferric oxide microspheres with positively charged surfaces

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Application publication date: 20120620