CN100522825C - Method for preparing magnetite Fe3O4 nano particles material - Google Patents
Method for preparing magnetite Fe3O4 nano particles material Download PDFInfo
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- CN100522825C CN100522825C CNB2007100576707A CN200710057670A CN100522825C CN 100522825 C CN100522825 C CN 100522825C CN B2007100576707 A CNB2007100576707 A CN B2007100576707A CN 200710057670 A CN200710057670 A CN 200710057670A CN 100522825 C CN100522825 C CN 100522825C
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- magnetite
- water
- sugar
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- nanoparticle
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Abstract
It is a method of preparing material of magnetite (Fe3O4) nanoparticle, which throws carbohydrate and ferrous sulfate solution into water to mix, adjusts PH value in alkali, and makes the mixture crystallize in hydrothermal condition of 100deg.C-300deg.C and prepares magnetite (Fe3O4) nanoparticle. Through changing the rate of carbohydrate and ferrous sulfate solution, PH value of the solution, temperature of crystallization or time of crystallization, you can control the size of the particle. You can prepare the magnetite (Fe3O4) nanoparticle whose size is from 4nm to 18nm utilizing the invention. The method of the invention has characters that operation is simple, needn't inactive gas to protect, productivity is high, material is convenient to obtain and its environment is good.
Description
[technical field]
The invention belongs to the synthetic field of magnetic nano-particle.In particular, relate to formation of iron based nanoparticles, the size control that especially has the magnetite nano particulate material of many important techniques application is synthesized.
[background technology]
Magnetite (Fe
3O
4) be three kinds of common ferriferous oxide FeO with many important application, Fe
2O
3, Fe
3O
4One of in, owing to have evenly adjustable magnetic property, Fe
3O
4Value has a wide range of applications in magnetic material field.The magnetic iron oxide nanoparticle dispersion that is known as " ferrofluid " on the market has been widely used in for example rotating shaft sealing of vacuum vessel, the vibration damping of electronic machine, avionics, robot technology, fields such as lathe and drive system location aware.Magnetite is typical semi-metal material, and its black particles dispersion has been used for printing industry, as high-quality toning agent or printing ink.The magnetite dispersion also is used to make liquid crystal device, color monitor for example, monochromatic ray switch and tunable wavelength filter etc.As the semi-conductor ferrimagnet with high-curie temperature (858K), magnetite also is applied in the production of tunnelling device.The magnetite nano particle is particularly rapid at the application development of biological association area.Particularly be applied to the nuclear magnetic resonance in the clinical medicine, drug delivery, clinical diagnosis and treatment, the AC magnetic field induction excitation of bioseparation and cancer etc.The magnetite nano particle that is applied to biological field generally should have the size that is lower than 30nm, narrow distribution of sizes, good dispersity, superparamagnetism, the characteristic that degree of crystallinity is high.
In the prior art, preparation magnetite nano particle mainly contains following several method.Prepare magnetic fluid by in ball mill, grinding magnetite for a long time with tensio-active agent and carrier solvent; Utilize ferrous iron (Fe
2+) and ferric iron (Fe
3+) the chemical precipitation reaction of ion in the aqueous solution obtain hyperfine magnetic oxide, and realize the strong adsorption of magnetic particle upper surface promoting agent in the aqueous solution.This method needs short preparation time than Ginding process, and the batch process of suitable magnetic fluid.But, must constantly adjust the pH value of solution so that guarantee the formation of particle and stable; The magnetite nano particle that the method preparation size of elevated temperature heat decomposition molysite is evenly distributed in organic solvent obtains the concern of wide method recently; Also has the ultrasonic/microwave preparation method simultaneously; Laser/X-ray diffraction method; The multipolymer template; Sol-gel method etc.But in all these technology, it is adjustable to be evenly distributed at preparation size, and production cost is low, and environmental friendliness and production in enormous quantities aspect all can not meet the demands, and need need to be resolved hurrily.
[summary of the invention]
The objective of the invention is to overcome the above deficiency that exists in the prior art, a kind of preparation magnetite Fe is provided
3O
4The method of nanometer particle material.
The invention provides a kind of synthetic Fe that is used for
3O
4The method of nanoparticle, this Fe
3O
4Nanoparticle has controllable particle diameter and distribution of sizes.As shown in Figure 1, by in water, pressing the mole number and the Fe of the reducing sugar that reducing sugar or hydrolyzable generate
3+The ratio of mole number add carbohydrate and molysite greater than 1:3, the water yield is a minimum with whole solubilizing reaction things, (energy ionization goes out one of alkali of OH-radical ion) regulates the pH value greater than 4 with alkali, and with mixture 100 ℃ to 300 ℃ crystallization 2h-4d under hydro-thermal state autogenous pressure, driving still is black liquor, and cool to room temperature (for example 15-30 ℃) is isolated the magnetic nano-particle of black afterwards with deionized water or DMF centrifuge washing, to remove impurity such as reacted by product, obtain pure Fe
3O
4Nanometer particle material.This black product is dispersed in the solvent, can prepares the magnetite nano particle dispersion of all kinds of SOLVENTS dispersive black.
Above-mentioned molysite is one of hydrolyzable trivalent iron salt, as FeCl
3, Fe (NO
3)
3Or Fe
2(SO
4)
3One of.
Carbohydrate comprises reducing sugar, or can be hydrolyzed to one of nonreducing sugar of reducing sugar under the respective acids condition behind the iron salt hydrolysis.
One of described solvent comprises water, alcohol, and acetone, alkane, aromatic solvent, or chlorinated solvents.
Tem analysis shows that particle has dispersion preferably, even size distribution.By changing the ratio of molysite and carbohydrate, change the concentration of alkali, crystallization temperature or crystallization time can be controlled the size of particle.Utilize the present invention to make size at the magnetite nano particle with narrow size distribution of 4nm in the 18nm scope.Fig. 6 is 4nm, 9nm, 12nm, 17nm Fe
3O
4The X-ray diffraction figure of particle, by X ray among the figure peak width at half height, can be by Scherrer formula assessment median size:
L＝Kλ/βcosθ
Wherein L is the average grain size along Miller indices (h k l) direction, and λ is the wavelength of used X ray, and K is the Scherrer constant, and its value is approximately 0.9, and θ is a Bragg angle, and β is a half-peak width.This calculating has confirmed that XRD calculates the size of particles of gained and by the TEM image being carried out the median size coupling that statistical study is determined, shows that each particle all is one crystal.
Because Fe
3O
4The small size of nanocrystal, therefore at room temperature they are superparamagnetism; Fig. 7 has provided 10nm Fe under the room temperature
3O
4The magnetic hysteresis loop of nano crystal material.
Advantage of the present invention and positively effect:
The present invention changes the pH value of solution by changing the ratio of carbohydrate and molysite, and crystallization temperature or crystallization time can be controlled the size of particle.Utilize the present invention to make size at the magnetite nano particle with narrow size distribution of 4nm in the 18nm scope.The inventive method of preparation magnetite nano particle has simple to operately, does not need protection of inert gas, and productive rate height, raw material are easy to get and eco-friendly characteristics.
[description of drawings]
Fig. 1 is the hydrolysis by molysite, the Fe of preparation
3O
4The general approach synoptic diagram of nanoparticle;
Fig. 2 is the 4nm Fe of preparation
3O
4The TEM image of particle;
Fig. 3 is the 9nm Fe of preparation
3O
4The TEM image of particle;
Fig. 4 is the 12nm Fe of preparation
3O
4The TEM image of particle;
Fig. 5 is the 17nm Fe of preparation
3O
4The TEM image of particle;
Fig. 6 is A) 4nm, B) 9nm, C) 12nm, D) the X-ray diffraction figure of 17nm nanocrystal;
Fig. 7 is 10nm Fe under the room temperature
3O
4The magnetic hysteresis loop of nano crystal material.
[embodiment]
Embodiment 1,4nm Fe
3O
4The preparation of particle.
1.8g FeCl
3Be dissolved in the 100g water of 60 ℃ of heating in water bath with 7.7g glucose, stir 2h, it is 11 that ammoniacal liquor is regulated the pH value, solution colour deepens brown, changes in the teflon-lined autoclave 110 ℃ of hydrothermal crystallizing 6h over to, cool to room temperature, open still and water centrifuge washing four times, thoroughly remove impurity, can get black magnetite nano particle.Again be scattered in the water, can prepare the magnetite nano dispersion.
Embodiment 2,9nm Fe
3O
4The preparation of particle.
8.86g Fe
2(SO4)
3Be dissolved in the 100g water of 60 ℃ of heating in water bath with 6.65g glucose, stir 1h, it is 10 that ammoniacal liquor is regulated the pH value, solution colour deepens brown, changes in the teflon-lined autoclave 130 ℃ of hydrothermal crystallizing 8h over to, cool to room temperature, open still and water centrifuge washing four times, thoroughly remove impurity, can get black magnetite nano particle.Again be scattered in the chlorinated solvents, can prepare the magnetite nano dispersion.
Embodiment 3,12nm Fe
3O
4The preparation of particle.
3.6g FeCl
3With the 13.3g sucrose dissolved in the 100g of 60 ℃ of heating in water bath water, stir 0.5h, it is 10 that ammoniacal liquor is regulated the pH value, solution colour deepens brown, changes in the teflon-lined autoclave 150 ℃ of hydrothermal crystallizing 12h over to, cool to room temperature, open still and water or DMF centrifuge washing four times, thoroughly remove impurity, can get black magnetite nano particle.Again be scattered in the aromatic solvent, can prepare the magnetite nano dispersion.
Embodiment 4,17nm Fe
3O
4The preparation of particle.
4.43g Fe
2(SO4)
3With the 6.65g sucrose dissolved in the 100g of 60 ℃ of heating in water bath water, stir 0.5h, it is 9 that ammoniacal liquor is regulated the pH value, solution colour deepens brown, changes in the teflon-lined autoclave 180 ℃ of hydrothermal crystallizing 48h over to, cool to room temperature, drive still and, thoroughly remove impurity, can get black magnetite nano particle with 60 ℃ of water or DMF centrifuge washing four times.Again be scattered in the alkane solvent, can prepare the magnetite nano dispersion.
Claims (7)
1, a kind of preparation magnetite Fe
3O
4The method of nanometer particle material comprises:
The first, in water, press the mole number and the Fe of the reducing sugar of reducing sugar or hydrolyzable generation
3+The ratio of mole number add sugar and molysite greater than 1:3, regulate pH value greater than 4 with alkali, the formation mixture;
The second, mixture is packed in the autoclave, crystallization 2h-4d under the hydro-thermal autogenous pressure, the hydrothermal crystallizing temperature is 100 ℃～300 ℃;
Three, with above-mentioned autoclave cool to room temperature, drive still;
Four, water or N, the dinethylformamide wash products, centrifugation makes magnetite Fe
3O
4Nanoparticle.
2, the method for claim 1 is characterized in that the magnetite Fe that above-mentioned the 4th step makes
3O
4Nanoparticle disperses in solvent, makes the nanocrystal dispersion.
3, method as claimed in claim 1 or 2 is characterized in that described molysite is one of hydrolyzable trivalent iron salt.
4, method as claimed in claim 3 is characterized in that described molysite is FeCl
3, Fe (NO
3)
3Or Fe
2(SO
4)
3One of.
5, method as claimed in claim 1 or 2 is characterized in that described steamed bun stuffed with sugar draws together reducing sugar, or can be hydrolyzed to one of nonreducing sugar of reducing sugar under the respective acids condition behind the iron salt hydrolysis.
6, method as claimed in claim 1 or 2 is characterized in that described alkali comprises that energy ionization go out OH
-One of alkali of radical ion.
One of 7, method as claimed in claim 2 is characterized in that described solvent comprises water, alcohol, and acetone, alkane, aromatic solvent, or chlorinated solvents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576707A CN100522825C (en) | 2007-06-19 | 2007-06-19 | Method for preparing magnetite Fe3O4 nano particles material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576707A CN100522825C (en) | 2007-06-19 | 2007-06-19 | Method for preparing magnetite Fe3O4 nano particles material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101070193A CN101070193A (en) | 2007-11-14 |
| CN100522825C true CN100522825C (en) | 2009-08-05 |
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ID=38897635
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100576707A Expired - Fee Related CN100522825C (en) | 2007-06-19 | 2007-06-19 | Method for preparing magnetite Fe3O4 nano particles material |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885512B (en) * | 2010-01-05 | 2012-02-15 | 河北医科大学 | Hydrothermal synthesis process of magnetic ferroferric oxide nanometer ultrafine particles in non-N2 atomosphere |
| CN103014216B (en) * | 2013-01-08 | 2015-06-24 | 中南大学 | Reduction method of iron compound in iron-containing material |
| CN103692519B (en) * | 2013-12-19 | 2015-10-21 | 东北林业大学 | A kind of wood surface growth in situ magnetic Nano Fe 3o 4method |
| CN104628073B (en) * | 2015-01-28 | 2016-08-17 | 天津城建大学 | A kind of preparation method of the Nanoscale Iron processed for waste water |
| CN105238924A (en) * | 2015-10-23 | 2016-01-13 | 辽宁科技大学 | Method for extracting aluminum and iron from high-iron diasporic bauxite |
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2007
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