CN103058283B - Preparation method of iron oxides with adjustable size, appearance and compositions - Google Patents

Preparation method of iron oxides with adjustable size, appearance and compositions Download PDF

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CN103058283B
CN103058283B CN201310038932.0A CN201310038932A CN103058283B CN 103058283 B CN103058283 B CN 103058283B CN 201310038932 A CN201310038932 A CN 201310038932A CN 103058283 B CN103058283 B CN 103058283B
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particle
molysite
sodium bicarbonate
oxide particle
iron oxides
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CN201310038932.0A
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Chinese (zh)
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CN103058283A (en
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杨萍
王丹
曹永强
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济南大学
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Abstract

The invention discloses a preparation method of iron oxides with adjustable size, appearance and compositions. The preparation method comprises the steps of: adding ferric salt, sodium bicarbonate and organic amine to an organic solvent, and stirring to obtain a transparent solution; and carrying out heat treatment on the solution, carrying out centrifugal separation, and washing to obtain the iron oxides particles. The iron oxides particles comprise ferric oxide particles and ferroferric oxide particles, have the diameter of 10-600nm, and are solid, meso-porous or hollowly spherical in appearance. The preparation method is simple in preparation process; the yield of the iron oxides is high; the size distribution of the products is narrow, and the products have high saturated magnetic field intensity; the iron oxides with different sizes, appearances and compositions can be obtained by simply controlling reaction conditions; and the preparation method is significant for preparation and application of the iron oxide particles.

Description

The preparation method of the iron oxide particle that a kind of size, pattern and composition are adjustable
Technical field
The present invention relates to a kind of preparation method of iron oxide particle, be specifically related to the preparation method of the adjustable iron oxide particle of a kind of size, pattern and composition.
Background technology
Ferriferous oxide comprises FeO, Fe 2o 3and Fe 3o 4, wherein Fe 2o 3and Fe 3o 4micro-nano granules has a wide range of applications.Fe 3 O 4 magnetic micro-and nano-particles is widely used in the fields such as magnetic fluid, Magnetic resonance imaging, biological medicine, data storage.Fe 2o 3micro-and nano-particles has application extremely widely in fields such as coating, electronic product, magnetic recording material, catalyzer and biomedical engineerings.The ferriferous oxide of hollow structure, because inner-cavity structure and the surfaces externally and internally with lower density, uniqueness make it have unique character, has very great application at aspects such as water treatment, biomarker and control release, catalysis.
The ferriferous oxide of preparing with solvent-thermal method at present both at home and abroad has that good crystallinity, output are high, magnetic saturation intensity advantages of higher.CN 201210158461.2 discloses a kind of method of controlling Z 250 pattern and performance, the transformation that being characterized in can be simply, method realizes ferriferrous oxide particles pattern efficiently.CN 200810062614.7 discloses the method for utilizing iron trichloride, methyl alcohol (or ethanol, ethylene glycol) and sodium hydroxide to prepare the ferriferrous oxide nano-particle of spheroidal particle as starting raw material.CN201010283732.8 discloses a kind of alpha-type ferric oxide micron ball and preparation method thereof, provides a kind of particle balling preparation rate high, distribution of sizes homogeneous, and there is the preparation method of the alpha-type ferric oxide micron ball of superior magnetic property.In addition, document " Peng Hu, Lingjie Yu, Ahui Zuo, Chenyi Guo, and Fangli Yuan. J. Phys. Chem. C, 2009,113,900 – 906 " has been reported the preparation of Z 250 hollow ball.
Gained granulometric composition and granule-morphology are certain according to the method described above, controlling reaction conditions only can make grain diameter size change, the composition and the pattern that change particle need to change preparation method, can not realize simply, efficiently the transformation of iron oxide particle size, pattern, composition.
Summary of the invention
The present invention is directed to the deficiency that existing method exists, this is proposed to improvement, the preparation method of the adjustable iron oxide particle of a kind of size, pattern and composition is provided, the selection of this preparation method by reaction conditions and control composition and the pattern that can simply, effectively change ferriferous oxide, is easy to control and realize.
Concrete technical scheme is as follows:
A preparation method for iron oxide particle, is characterized in that: described iron oxide particle is ferric oxide particle or ferriferrous oxide particles, comprises the following steps:
(1) molysite, sodium bicarbonate, organic amine are joined in organic solvent, stir and obtain clear solution;
(2) solution step (1) being made into is heat-treated, and prepares ferriferous oxide;
(3), by reaction solution centrifugation, washing, gained throw out is iron oxide particle.
In aforesaid method, halogenide, vitriol or nitrate that described molysite is iron, such as FERRIC CHLORIDE ANHYDROUS, Iron(III) chloride hexahydrate, ferric sulfate, iron nitrate etc.
In aforesaid method, described organic amine is quadrol, propylene diamine, butanediamine or thanomin.
In aforesaid method, can be by controlling the particle of choosing to obtain different compositions of organic solvent, while preparing ferric oxide particle, described organic solvent is methyl alcohol, ethanol, propyl alcohol, butanols or Virahol; While preparing ferriferrous oxide particles, described organic solvent is ethylene glycol, propylene glycol, butyleneglycol or glycerol.
In aforesaid method, the mol ratio of molysite and sodium bicarbonate is 1:0.3-8, can obtain the particulate matter of different-shape with magnitude relation by what control molysite and sodium bicarbonate, in the time that the mol ratio of molysite and sodium bicarbonate is 1:0.3 ~ 2.9, gained iron oxide particle is solid spherical; Mol ratio is 1:3 ~ 5 o'clock, and gained iron oxide particle is mesoporous sphere; Mol ratio is 1:5 ~ 8 o'clock, and gained iron oxide particle is hollow ball shape.
In aforesaid method, the mol ratio of molysite and organic amine is 0.9 ~ 36:1.
In aforesaid method, the volume ratio of organic solvent and organic amine is 1:0.005 ~ 0.2.
In aforesaid method, gained particulate matter diameter is within the scope of 10 ~ 600 nm, and granular size can be by use magnitude relation, the heat-treat condition control of organic solvent and organic amine.Heat-treating methods is solvent-thermal method or microwave method, and heat treated temperature is 150-260 ℃, and the heat treated time is generally 4 ~ 24h.Generally, obtain the particle of a certain size, on the basis of fixing other conditions, the low required time of thermal treatment temp is longer, and the high required time of thermal treatment temp is shorter.
The present invention utilizes solvent-thermal method or microwave method to prepare simply efficiently size, pattern, spherical iron oxide particle that composition is adjustable.By controlling reaction conditions, obtain diameter at the difference composition of 10 ~ 600 nm scopes, the iron oxide particle of different-shape.In present method, can obtain the iron oxide particle of different compositions by changing the kind of organic solvent; By changing the ratio of molysite and sodium bicarbonate, can obtain the iron oxide particle of different-shape; By adjusting ratio and temperature of reaction and the time of organic amine and organic solvent, can control the size of iron oxide particle.Reaction controllability is strong, product production high (productive rate reaches more than 90%), and magnetic saturation intensity high (being about 65 ~ 85 emu/g), particulate component, morphology change boundary line are clear and definite, are easy to manipulation and realize.
Preparation technology of the present invention is simple, production cost is low, Modulatory character is strong, can obtain the iron oxide particle of different size, pattern, composition by simple control reaction conditions, products therefrom narrow diameter distribution, output is high, purity is high, saturation magnetic field intensity is high, have application extremely widely in fields such as magnetic recording material, catalyzer, biomedical engineering, Magnetic resonance imaging, data storages, this invents the preparation to ferriferous oxide ball and applies significant.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) picture of the synthetic solid Z 250 of the embodiment of the present invention 1.
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the synthetic solid Z 250 of the embodiment of the present invention 1.
Fig. 3 is the magnetic hysteresis loop collection of illustrative plates of the synthetic solid Z 250 of the embodiment of the present invention 1.
Fig. 4 is the particle size distribution figure of the synthetic solid Z 250 of the embodiment of the present invention 1.
Fig. 5 is transmission electron microscope (TEM) picture of the synthetic mesoporous ferriferrous oxide of the embodiment of the present invention 2.
Fig. 6 is the particle size distribution figure of the synthetic mesoporous ferriferrous oxide of the embodiment of the present invention 2.
Fig. 7 is transmission electron microscope (TEM) picture of the synthetic hollow Z 250 of the embodiment of the present invention 3.
Fig. 8 is transmission electron microscope (TEM) picture of the synthetic solid Z 250 of the embodiment of the present invention 4.
Fig. 9 is the magnetic hysteresis loop collection of illustrative plates of the synthetic solid Z 250 of the embodiment of the present invention 4.
Figure 10 is transmission electron microscope (TEM) picture of the synthetic hollow Z 250 of the embodiment of the present invention 5.
Figure 11 is transmission electron microscope (TEM) picture of the synthetic hollow ferric oxide of the embodiment of the present invention 6.
Figure 12 is X-ray diffraction (XRD) collection of illustrative plates of the synthetic hollow ferric oxide of the embodiment of the present invention 6.
Embodiment
Below by embodiment, the present invention will be further elaborated, and following explanation only, in order to explain the present invention, does not limit its content.
embodiment 1
1.1 join the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 0.45 g, 1 mL quadrol in 30 mL ethylene glycol and stir to clarify;
1.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 16 hours;
1.3 after reaction finishes, obtain solid Z 250 particle after centrifugation and washing.The diameter of particle is 320 nm, and X-ray diffraction characterizes and proves Z 250, and magnetic saturation intensity is that 78.95 emu/g. particle diameters are even.Respectively as shown in Figure 1,2,3, 4.The output of sample is 92.3%.
embodiment 2
2.1 join the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 1 g, 1.5 mL propylene diamine in 30 mL propylene glycol and stir to clarify;
2.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 16 hours;
2.3 after reaction finishes, obtain mesoporous Z 250 particle after centrifugation and washing.The diameter of particle is about 120 nm.As shown in Figure 5,6.The specific surface area of mesoporous Z 250 particle is 78 m 2g -1, mean pore size is 18 nm.The output of sample is 92.7%.
embodiment 3
3.1 join the quadrol of the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 1.10 g, 0.15 mL in 30 mL glycerol and stir to clarify;
3.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 20 hours;
After 3.3 reactions finish, after centrifugation and washing, obtain hollow Z 250 particle.The diameter of particle is about 260 nm.As shown in Figure 7.The output of sample is 90.6%.
embodiment 4
4.1 join the quadrol of the sodium bicarbonate of the Fe(NO3)39H2O of 1.010 g, 0.6 g, 0.25 mL in 30 mL ethylene glycol and stir to clarify;
4.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 10 hours;
After 4.3 reactions finish, after centrifugation and washing, obtain solid Z 250 particle.Particle dia is about 30 nm, and magnetic saturation intensity is 70.33 emu/g.Respectively as shown in Figure 8,9.The output of sample is 90.9%.
embodiment 5
5.1 join the quadrol of the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 1.1g, 0.15 mL in 30 mL ethylene glycol and stir to clarify;
5.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 14.5 hours;
5.3 after reaction finishes, obtain hollow Z 250 particle after centrifugation and washing.Particle dia is about 200 nm.As shown in figure 10.The output of sample is 90.3%.
embodiment 6
6.1 join the quadrol of the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 1.08 g, 0.2 mL in 30 mL propyl alcohol and stir to clarify;
6.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 17 hours;
After 6.3 reactions finish, after centrifugation and washing, obtain hollow ferric oxide particle.Particle dia is about 100 nm, and X-ray diffraction characterizes and proves ferric oxide.Respectively as shown in Figure 11,12.The output of sample is 90.9%.
embodiment 7
7.1 join the butanediamine of the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 0.65 g, 2 mL in 30 mL butyleneglycols and stir to clarify;
7.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 15 hours;
7.3 after reaction finishes, obtain mesoporous Z 250 particle after centrifugation and washing.The diameter of particle is about 110 nm.The specific surface area of mesoporous Z 250 particle is 73 m 2g -1, mean pore size is 16 nm.The output of sample is 91.5%.
embodiment 8
8.1 by the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 0.07 g, and the thanomin of 3 mL joins in 30 mL ethylene glycol and stirs to clarify;
8.2 above-mentioned solution is transferred in reactor, is reacted at 155 ℃ 12 hours;
After 8.3 reactions finish, after centrifugation and washing, obtain solid Z 250 particle.The diameter of particle is about 150 nm.The output of sample is 92.0%.
embodiment 9
9.1 by the sodium bicarbonate of the ferric sulfate of 1.2 g (III), 0.21 g, and the thanomin of 2 mL joins in 30 mL ethylene glycol and stirs to clarify;
9.2 above-mentioned solution is transferred in reactor, is reacted at 260 ℃ 10 hours;
After 9.3 reactions finish, after centrifugation and washing, obtain solid Z 250 particle.The diameter of particle is about 210 nm.The output of sample is 90.2%.
embodiment 10
10.1 join the quadrol of the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 1.2 g, 6 mL in 30mL propylene glycol and stir to clarify;
10.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 18 hours;
10.3 after reaction finishes, obtain hollow Z 250 particle after centrifugation and washing.The diameter of particle is about 80 nm.The output of sample is 93.1%.
embodiment 11
11.1 join the butanediamine of the sodium bicarbonate of the ferric chloride hexahydrate of 0.676 g, 0.6 g, 0.5 mL in 25 mL methyl alcohol and stir to clarify;
11.2 above-mentioned solution is transferred in reactor, is reacted at 200 ℃ 14 hours;
11.3 after reaction finishes, obtain solid ferric oxide particle after centrifugation and washing.The diameter of particle is about 80 nm.The output of sample is 90.7%.

Claims (4)

1. a preparation method for iron oxide particle, is characterized in that: described iron oxide particle is ferric oxide particle or ferriferrous oxide particles, comprises the following steps:
(1) molysite, sodium bicarbonate, organic amine are joined in organic solvent, stir and obtain clear solution;
(2) solution step (1) being made into is heat-treated, and prepares ferriferous oxide;
(3) by reaction solution centrifugation, washing, gained throw out is iron oxide particle, and described iron oxide particle pattern is the spheroidal particle of solid, mesoporous or hollow structure;
While preparing ferric oxide particle, described organic solvent is methyl alcohol, ethanol, propyl alcohol, butanols or Virahol; While preparing ferriferrous oxide particles, described organic solvent is ethylene glycol, propylene glycol, butyleneglycol or glycerol;
While preparing full particle, the mol ratio of molysite and sodium bicarbonate is 1:0.3 ~ 2.9; While preparing mesoporous particles, the mol ratio of molysite and sodium bicarbonate is 1:3 ~ 5, does not comprise 1:5; While preparing hollow bead, the mol ratio of molysite and sodium bicarbonate is 1:5 ~ 8;
The volume ratio of organic solvent and organic amine is 1:0.005 ~ 0.2;
In step (2), heat-treating methods is solvent-thermal method or microwave method, and heat treated temperature is 150-260 ℃, and the heat treated time is 4 ~ 24h.
2. preparation method according to claim 1, is characterized in that: halogenide, vitriol or nitrate that described molysite is iron; Described organic amine is quadrol, propylene diamine, butanediamine or thanomin.
3. preparation method according to claim 1, is characterized in that: the mol ratio of molysite and organic amine is 0.9 ~ 36:1.
4. preparation method according to claim 1, is characterized in that: particle diameter is 10 ~ 600 nm.
CN201310038932.0A 2013-02-01 2013-02-01 Preparation method of iron oxides with adjustable size, appearance and compositions CN103058283B (en)

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CN103274477B (en) * 2013-06-07 2015-02-11 三明学院 Preparation method of superparamagnetic Fe3O4 microspheres
CN103480324B (en) * 2013-09-29 2015-09-23 中南大学 A kind of mesoporous Fe 3o 4microballoon and methods for making and using same thereof
CN103663571A (en) * 2013-12-24 2014-03-26 武汉理工大学 Preparation method for superparamagnetism ferroferric oxide sub-micron hollow microsphere
CN103801263B (en) * 2013-12-26 2016-01-06 华南师范大学 One utilizes iron and steel pickling waste liquid to prepare EDA-Fe 3o 4the method of nano particle and application
CN103708564B (en) * 2014-01-03 2015-06-24 南昌航空大学 Solvothermal method for preparing nano ferroferric oxide powder
CN104058465B (en) * 2014-07-21 2016-03-02 济南大学 A kind of Z 250 hollow polyhedral particle and preparation method thereof
CN105502513A (en) * 2015-12-23 2016-04-20 淮北师范大学 Preparation method of hollow ferroferric oxide wave-absorbing material
WO2018187924A1 (en) * 2017-04-11 2018-10-18 深圳市佩成科技有限责任公司 Method for preparing fe2o3 having hollow structure based on hydrothermal synthesis
CN107628648A (en) * 2017-09-13 2018-01-26 清华大学 A kind of preparation method of pattern and the controllable ferric oxide particles of size
CN110379636B (en) * 2019-06-06 2021-05-11 东南大学 Preparation of Zn ion doped Fe3O4Method for preparing hollow sphere-graphene electrode material
CN111589186A (en) * 2020-06-02 2020-08-28 林多炉 Magnetic super-hydrophobic polyurethane sponge oil-water separation material and preparation method thereof

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CN102765761B (en) * 2012-07-03 2014-05-21 吉林大学 Method for preparing ferroferric oxide at room temperature

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