CN101538068A - Method for preparing monodisperse Fe3O4 magnetic nanoparticles - Google Patents
Method for preparing monodisperse Fe3O4 magnetic nanoparticles Download PDFInfo
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- CN101538068A CN101538068A CN200910066904A CN200910066904A CN101538068A CN 101538068 A CN101538068 A CN 101538068A CN 200910066904 A CN200910066904 A CN 200910066904A CN 200910066904 A CN200910066904 A CN 200910066904A CN 101538068 A CN101538068 A CN 101538068A
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Abstract
The invention provides a method for preparing monodisperse Fe3O4 magnetic nanoparticles. Precursor is Fe2O3 or iron oxide yellow which has the chemical formula of Fe2O3.H2O; stabilizing agent is oleic acid; high temperature organic solvent is 1-octadecylene (b. p. 318DEG C); precipitating agent is prepared by mixing any two of toluene, dimethyl benzene, ethanol, isopropanol and acetone according to the volume ratio of 1:4-2:3; the mol ratio between the precursor and the stabilizing agent is 1:4-1:9; the mol ratio between the precursor and the high temperature organic solvent is 1:10; inert gas protection is not needed, and the Fe3O4 magnetic nanoparticles which have small sizes, monodisperse, narrow distribution, high saturation magnetization intensity and superparamagnetism. The method can be widely applied to biomedicine fields such as magnetic resonance imaging, biological magnetic separation, magnetic target drug carrier, biological magnetic marker and the like, and the high technical fields such as magnetic sealing, aerospace lubrication, magnetic anti-counterfeiting ink material, etc.
Description
Technical field
The present invention relates to a kind of single Fe of dispersion
3O
4The preparation method of magnetic nano-particle.
Background technology
Magnetic ferric oxide nano particles gains great popularity and payes attention in the application (as nuclear magnetic resonance, magnetic thermotherapy, the separation of biological magnetic, magnetic target medicine carrier etc.) of biomedical sector because of its special magnetic performance.The size of magnetic ferric oxide nano particles, distribution of sizes, monodispersity quality and magnetic responsiveness height are most important to its biomedical applications, because undersized magnetic nano-particle has and virus (20-450nm), protein (5-50nm), DNA or gene (2nm is wide and 10-100nm long) the comparable size of yardstick, thereby be suitable for combining and form magnetic marker with these biological units; The monodispersity of magnetic nano-particle and narrow distribution can provide the target medicine carrier of physics, chemistry and biological property much at one for the research of aspects such as in vivo distribution of medicine, pharmacokinetics; High saturation and magnetic intensity helps improving the operability of magnetic control and reduces magnetic nano-particle because of magnetic loss that finishing caused; Super paramagnetic nano particle can be eliminated magnetic reunion etc. fully.
Yet the magnetic ferric oxide nano particles preparation of small size, single dispersion, narrow distribution, high saturation and magnetic intensity and superparamagnetism etc. is the bottleneck of its biomedical applications of restriction always.Because the common particle diameter of magnetic nano-particle of adopting using vaporization condensation process, grind method, physics method method such as machine-alloying being prepared is big and distribute widely, and the magnetic nano-particle size distribution that chemical method is prepared as coprecipitation method commonly used is wide, it is big or small and the stable system pH that depends on consumingly; The magnetic nano-particle particle diameter ratio that sol-gel method is prepared is more even, but crystallinity is poor, a little less than the magnetic responsiveness; Though hydrothermal synthesis method crystallinity and magnetic responsiveness are good, need High Temperature High Pressure and be difficult to obtain the monodispersed magnetic nano-particle of small particle size, or the like.In order to solve an above-mentioned difficult problem, people are developed the method for organic synthesis, and the metal organic precursor body heat of exploring magnetic nano-particle is decomposed synthetic method, for example, Sun S. etc. with oleic acid and oleyl amine as stabilizing agent, with 1,2-hexadecane glycol as reducing agent, by thermal decomposition ferric acetyl acetonade Fe (acac) in organic phase
3Method and seeded growth method synthesize particle diameter at the adjustable single Fe of dispersion of 5-20nm scope
3O
4Magnetic nano-particle.(Sun?S，Zeng?H.J.Am.Chem.Soc.，2002，124(28)：8204-8205.)。Brilliant grade far away is under the nitrogen atmosphere protection, by selecting high boiling 2-Pyrrolidone and derivative intensive polar solvent high temperature thermal decomposition Fe (acac) thereof
3, Fe (CO)
5, FeCup
3With the inorganic molysite predecessor, take ethylene glycol and derivative thereof as stabilizing agent, successfully prepare the Fe of monodisperse water soluble
3O
4Nano particle (Chinese patent application number: 03136275.3 and 03136273.7).FeOOH and Fe (OH) that the employings such as Yu W.W. are sieved
3Be source of iron, then, it be dissolved in the oleic acid, again under inert gas shielding in 1-octadecylene solvent 320 ℃ of thermal decompositions of high temperature obtain adjustable single Fe of dispersion from 6nm to 30nm
3O
4Magnetic nano-particle (Yu WW, Falkner J C, Yavuz C T, et al.Chem.Commun.2004,2306-2307.).In above-mentioned these preparation methods, it is somewhat expensive (as, Fe (acac) to exist reagent
3, 1,2-n-Hexadecane two pure and mild oleyl amines etc.) and poisonous (as Fe (CO)
5, 2-Pyrrolidone etc.) and need sieve and shortcoming or deficiency such as nitrogen protection.Therefore, develop the inexpensive list nontoxic, that synthesis technique simple, the single sintering amount is big, particle diameter is controlled of a kind of raw material and disperse Fe
3O
4The preparation method of magnetic nano-particle will have broad application prospects and market prospects.
Summary of the invention
The invention provides a kind of single Fe of dispersion
3O
4The preparation method of magnetic nano-particle.Its condition and step are as follows:
Predecessor is Fe
2O
3Or iron oxide yellow, the chemical formula of iron oxide yellow is Fe
2O
3H
2O; Stabilizing agent is oleic acid; The high temperature organic solvent is 1-octadecylene (b.p.318 ℃); Precipitating reagent is that any two kinds of 1: 4 by volume～2: 3 mixed preparing in toluene, dimethylbenzene, ethanol, isopropyl alcohol and the acetone form; Predecessor: the mol ratio of stabilizing agent is 1: 4～1: 9; Predecessor: the mol ratio of high temperature organic solvent is 1: 10;
According to proportioning, predecessor, stabilizing agent and high temperature organic solvent are added in three mouthfuls of reactors, install air set pipe, then, magnetic agitation, and in 280-320 ℃ of reaction 2-10 hour, after reaction finishes, naturally cool to room temperature, then add precipitating reagent, ultrasonic processing 20 minutes is after separating with permanent magnet or centrifuge again, obtain the precipitation of black, so far be called separating step; Repeated isolation step twice, the black precipitate that obtains obtain a kind of single Fe of dispersion 50-80 ℃ of lower oven dry
3O
4Magnetic nano-particle.Its particle diameter is adjustable in the 5-25nm scope, sees that Fig. 1 and Fig. 2 are transmission electron microscope photos.
The parting liquid that separating step is obtained is collected together, and parting liquid is recycled and obtained corresponding organic solvent after distillation or decompression distillation separation.
Beneficial effect: the invention provides a kind of single Fe of dispersion
3O
4The preparation method of magnetic nano-particle selects Fe
2O
3Reagent or commercial iron oxide yellow (Fe
2O
3H
2O) pigment need not inert gas shielding as predecessor, prepares the Fe of small size, single dispersion, narrow distribution, high saturation and magnetic intensity and superparamagnetism
3O
4Magnetic nano-particle can be widely used in the biomedical sector such as magnetic resonance imaging, the separation of biological magnetic, magnetic target medicine carrier, biological magnetic mark and magnetic seals, space flight is lubricated and the high-tech sector such as magnetic anti-forge printing ink material.Compared with prior art, have that raw material non-toxic inexpensive, synthesis technique are simple, inert-free gas protection, steady quality, productive rate is high and single advantage such as adjustable grain of disperseing.
Description of drawings
Fig. 1. with iron oxide yellow (Fe
2O
3H
2O) Fe for preparing for predecessor
3O
4The transmission electron microscope of magnetic nano-particle (TEM) photo.
Fig. 2. with Fe
2O
3Fe for the predecessor preparation
3O
4The transmission electron microscope of magnetic nano-particle (TEM) photo.
Fig. 3 .Fe
3O
4The XRD spectra of magnetic nano-particle and standard card.
Fig. 4 .Fe
3O
4Magnetic nano-particle hysteresis curve figure at room temperature.
Embodiment
Embodiment 1
According to predecessor: the mol ratio of stabilizing agent is 1: 4, predecessor: the mol ratio of high temperature organic solvent is 1: 10, accurately takes by weighing predecessor iron oxide yellow (Fe
2O
3H
2O) 10mmol, stabilizing agent oleic acid 40mmol and high temperature organic solvent 1-octadecylene 100mmol (35.5mL) add in the 250mL there-necked flask reactor, install air set pipe, then, magnetic agitation, in 320 ℃ of reactions 10 hours, reaction naturally cooled to room temperature after finishing.Then, add the toluene of 180mL and the precipitation agent of dehydrated alcohol mixing solutions (volume ratio is 1: 2), supersound process 20 minutes after separating with permanent magnet or whizzer, obtains the precipitation of black again, so far is called separating step; Repeated isolation step twice, the black precipitate that obtains is 50 ℃ of oven dry down.The about 1.5g of its output, product F e
3O
4The about 8nm of the average grain diameter of magnetic nano-particle.
Embodiment 2
According to predecessor: the mol ratio of stabilizing agent is 1: 7, predecessor: the mol ratio of high temperature organic solvent is 1: 10, accurately takes by weighing predecessor iron oxide yellow (Fe
2O
3H
2O) 10mmol, stabilizing agent oleic acid 70mmol and high temperature organic solvent 1-octadecylene 100mmol (35.5mL) add in the 250mL there-necked flask reactor, install air set pipe, then, magnetic agitation, in 300 ℃ of reactions 6 hours, reaction naturally cooled to room temperature after finishing.Then, add the toluene of 180mL and the precipitation agent of isopropyl alcohol mixture (volume ratio is 1: 3), supersound process 20 minutes after separating with permanent magnet or whizzer, obtains the precipitation of black again, so far is called separating step; Repeated isolation step twice, the black precipitate that obtains is 50 ℃ of oven dry down.The about 1.3g of its output, product F e
3O
4The about 17nm of the average grain diameter of magnetic nano-particle.
Embodiment 3-14: the according to the form below parameter is implemented, and working method is with embodiment 1 or 2.
Example 3-14 parameter list
| The embodiment numbering | Iron oxide yellow Fe 2O 3H 2O mmol | Fe 2O 3Mmol | Oleic acid mmol | 1-octadecylene mmol | Reaction temperature ℃ | Reaction time h | Mixed precipitant v/v | Baking temperature ℃ |
| 3 | 10 | - | 40 | 100 | 320 | 10 | Toluene and absolute ethyl alcohol 1/2 | 50 |
| 4 | 10 | - | 50 | 100 | 310 | 8 | Dimethylbenzene and isopropyl alcohol 1/3 | 70 |
| 5 | 10 | - | 60 | 100 | 300 | 6 | Acetone and absolute ethyl alcohol 2/3 | 70 |
| 6 | 10 | 70 | 100 | 290 | 5 | Toluene and isopropyl alcohol 1/4 | 80 | |
| 7 | 10 | - | 80 | 100 | 280 | 4 | Acetone and isopropyl alcohol 2/5 | 60 |
| 8 | 10 | - | 90 | 100 | 320 | 2 | Dimethylbenzene and | 60 |
| Acetone 1/3 | ||||||||
| 9 | - | 10 | 40 | 100 | 320 | 10 | Toluene and absolute ethyl alcohol (1/2) | 50 |
| 10 | - | 10 | 50 | 100 | 310 | 8 | Dimethylbenzene and isopropyl alcohol (1/3) | 70 |
| 11 | - | 10 | 60 | 100 | 300 | 6 | Acetone and absolute ethyl alcohol (2/3) | 70 |
| 12 | - | 10 | 70 | 100 | 290 | 5 | Toluene and isopropyl alcohol (1/4) | 80 |
| 13 | - | 10 | 80 | 100 | 280 | 4 | Acetone and isopropyl alcohol (2/5) | 60 |
| 14 | - | 10 | 90 | 100 | 320 | 2 | Dimethylbenzene and acetone (1/3) | 60 |
Claims (2)
1, a kind of single Fe that disperses
3O
4The preparation method of magnetic nano-particle is characterized in that condition and step are as follows:
Predecessor is Fe
2O
3Or iron oxide yellow, the chemical formula of iron oxide yellow is Fe
2O
3H
2O; Stabilizing agent is oleic acid; The high temperature organic solvent is the 1-octadecylene; Precipitating reagent is that any two kinds of 1: 4 by volume～2: 3 mixed preparing in toluene, dimethylbenzene, ethanol, isopropyl alcohol and the acetone form; Predecessor: the mol ratio of stabilizing agent is 1: 4～1: 9; Predecessor: the mol ratio of high temperature organic solvent is 1: 10;
According to proportioning, predecessor, stabilizing agent and high temperature organic solvent are added in three mouthfuls of reactors, install air set pipe, then, magnetic agitation, and in 280-320 ℃ of reaction 2-10 hour, after reaction finishes, naturally cool to room temperature, then add precipitating reagent, ultrasonic processing 20 minutes is after separating with permanent magnet or centrifuge again, obtain the precipitation of black, so far be called separating step; Repeated isolation step twice, the black precipitate that obtains obtain a kind of single Fe of dispersion 50-80 ℃ of lower oven dry
3O
4Magnetic nano-particle.
2, described a kind of single Fe that disperses as claimed in claim 1
3O
4The preparation method of magnetic nano-particle is characterized in that, the parting liquid that described separating step is obtained is collected together, and parting liquid is recycled and obtained corresponding organic solvent after distillation or decompression distillation separation.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698737B (en) * | 2009-10-28 | 2011-04-20 | 山东轻工业学院 | Method for preparing organic/inorganic nano magnetic composite materials |
| CN102675537A (en) * | 2012-04-06 | 2012-09-19 | 江苏大学 | Preparation method of magnetic material for removing dibenzothiophene from oil |
| JP2013529677A (en) * | 2010-06-29 | 2013-07-22 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Synthesis of high performance iron oxide particle tracer for magnetic particle imaging (MPI) |
| CN103979612A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Method for preparing triiron tetraoxide nanometer particles |
| CN104021411A (en) * | 2014-05-30 | 2014-09-03 | 江苏多维科技有限公司 | Magnetic anti-counterfeiting mark and identification system thereof |
| JP2014208569A (en) * | 2013-03-27 | 2014-11-06 | アイシン精機株式会社 | METHOD FOR MANUFACTURING FeO NANOPARTICLES, METHOD FOR FORMING CARBON NANOTUBES, AND FeO NANOPARTICLES |
| CN104140127A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院过程工程研究所 | Method for producing ferriferrous oxide by using ferric oxide as raw material |
| CN109879326A (en) * | 2019-03-22 | 2019-06-14 | 信阳师范学院 | A method of ferric oxide nanometer particle is prepared using tealeaves |
| CN112142115A (en) * | 2019-06-27 | 2020-12-29 | 南京中科拜尔医学技术有限公司 | Preparation method of superparamagnetic micron-sized magnetic beads |
| CN113371761A (en) * | 2020-03-09 | 2021-09-10 | 天津理工大学 | Preparation method and application of ferroferric oxide nanoparticles |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698737B (en) * | 2009-10-28 | 2011-04-20 | 山东轻工业学院 | Method for preparing organic/inorganic nano magnetic composite materials |
| JP2013529677A (en) * | 2010-06-29 | 2013-07-22 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Synthesis of high performance iron oxide particle tracer for magnetic particle imaging (MPI) |
| CN102675537A (en) * | 2012-04-06 | 2012-09-19 | 江苏大学 | Preparation method of magnetic material for removing dibenzothiophene from oil |
| CN102675537B (en) * | 2012-04-06 | 2014-08-20 | 江苏大学 | Preparation method of magnetic material for removing dibenzothiophene from oil |
| JP2014208569A (en) * | 2013-03-27 | 2014-11-06 | アイシン精機株式会社 | METHOD FOR MANUFACTURING FeO NANOPARTICLES, METHOD FOR FORMING CARBON NANOTUBES, AND FeO NANOPARTICLES |
| CN104140127A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院过程工程研究所 | Method for producing ferriferrous oxide by using ferric oxide as raw material |
| CN104140127B (en) * | 2013-05-09 | 2015-09-30 | 中国科学院过程工程研究所 | A kind of take ferric oxide as the method for raw material production Z 250 |
| CN103979612A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Method for preparing triiron tetraoxide nanometer particles |
| CN103979612B (en) * | 2014-05-23 | 2015-12-09 | 苏州大学 | A kind of method preparing ferriferrous oxide nano-particle |
| CN104021411A (en) * | 2014-05-30 | 2014-09-03 | 江苏多维科技有限公司 | Magnetic anti-counterfeiting mark and identification system thereof |
| CN104021411B (en) * | 2014-05-30 | 2017-11-24 | 江苏多维科技有限公司 | A kind of magnetic anti-counterfeiting mark and its identifying system |
| CN109879326A (en) * | 2019-03-22 | 2019-06-14 | 信阳师范学院 | A method of ferric oxide nanometer particle is prepared using tealeaves |
| CN112142115A (en) * | 2019-06-27 | 2020-12-29 | 南京中科拜尔医学技术有限公司 | Preparation method of superparamagnetic micron-sized magnetic beads |
| CN113371761A (en) * | 2020-03-09 | 2021-09-10 | 天津理工大学 | Preparation method and application of ferroferric oxide nanoparticles |
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Open date: 20090923 |