CN100355661C - Method for preparing polar solvent soluble nano ferriferrous oxide granule - Google Patents
Method for preparing polar solvent soluble nano ferriferrous oxide granule Download PDFInfo
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- CN100355661C CN100355661C CNB2005101110141A CN200510111014A CN100355661C CN 100355661 C CN100355661 C CN 100355661C CN B2005101110141 A CNB2005101110141 A CN B2005101110141A CN 200510111014 A CN200510111014 A CN 200510111014A CN 100355661 C CN100355661 C CN 100355661C
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- polar solvent
- ferriferrous oxide
- amine
- nano ferriferrous
- oxide granule
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Abstract
The present invention relates to a method for preparing nano ferroferric oxide granules which can dissolve in a polar solvent, which belongs to the field of nanotechnology. The method comprises the following steps: step 1, FeCl3.6H2O and FeCl2.4H2O are weighed and dissolved in water to obtain a molysite solution, wherein the mol ratio of the FeCl3.6H2O to the FeCl2.4H2O is 2: 1; step 2, amine which can dissolve in a non-polar solvent easily is weighed by a measuring cylinder and is dissolved in the non-polar solvent to obtain the mixed solution of an amine /non-polar solvent; step 3, the molysite solution is dripped into the mixed solution of the amine /non-polar solvent under the protection of nitrogen to carry out sustained reaction; step 4, after reaction products are taken out, sediment is obtained through a centrifugation method and is washed by acetone and deionized water, and black powder, namely nano ferroferric oxide granules, is obtained after vacuum freeze drying. The granules obtained through the present invention have good dispersancy in water and various polar solvents, the particle diameter distribution is uniform, the surfaces of the granules have certain electronic charges, which is favorable for wrapping polymers on the granules, and the granules have high saturation magnetization intensity and superparamagnetism.
Description
Technical field
What the present invention relates to is a kind of method of field of nanometer technology, specifically is the method that a kind of preparation dissolves in the nano ferriferrous oxide granule of polar solvent.
Background technology
In recent years, because magnetic nanoparticle extensive prospect in actual applications, the preparation method of relevant magnetic nanoparticle and the research of character have been subjected to very big attention.Aspect magnetic recording material, magnetic nanoparticle is expected to replace traditional micron order magnetic, is used for the high density magnetic recording material; At biological field, the magnetic microsphere made from magnetic Nano material can be widely used in the magnetic resonance radiography imaging, pharmaceutical carrier, thermotherapy and cell and proteinic aspect such as separate.The preparation method of nano ferriferrous oxide granule has multiple, can be divided into wet method and dry method generally.Wet method is many to be raw material with iron protochloride and iron(ic) chloride, adopts coprecipitation method, hydrothermal method, sol-gel method and microemulsion method preparation; Dry method is often with iron carbonyl [Fe (CO)
5] wait and be raw material, adopt methods preparations such as vapour deposition, thermolysis.Above preparation method is each has something to recommend him, and the demand difference can adopt different preparation methods.
Find through literature search prior art, chemical coprecipitation is the simplest a kind of method that directly can obtain nano ferriferrous oxide granule in a large number, deliver the article that is entitled as " Ordered two-dimensional arrays of ferritenanoparticles " (" the sequential 2 D array of ferrite nanometer particle ") for 1158 pages as magazine " Advanced Materials " (" advanced material ") calendar year 2001 the 13rd volume, adopt iron protochloride and iron(ic) chloride mixed solution, slowly splash in ammoniacal liquor or the sodium hydroxide solution, and obtain ferriferrous oxide particles.The main drawback of this method is: 1. the reaction of carrying out in the aqueous environment, and speed of response is fast, and the particle of acquisition is big, and skewness; 2. Zhi Bei ferriferrous oxide particles has water repellent surface, and under the situation that does not add other tensio-active agents or polymer protection, particle is very easily reunited, and is difficult to obtain finely disseminated particle in water.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide a kind of preparation to dissolve in the method for the nano ferriferrous oxide granule of polar solvent, make it in the advantage that the former chemical coprecipitation of reservation can prepare in a large number, with short production cycle, can obtain the scattered ferriferrous oxide particles of high purity fine particle.
The present invention is achieved by the following technical solutions, and the present invention adopts the coprecipitation method on water/oily interface to prepare, and may further comprise the steps:
(1) takes by weighing FeCl
36H
2O and FeCl
24H
2O, its mol ratio is 2: 1, is dissolved in 10～1000ml water, obtains iron salt solutions;
(2) graduated cylinder is measured the oil-soluble amine that 2～50ml easily is dissolved in non-polar solvent, is dissolved in 30～1000ml non-polar solvent, and the mixing that obtains amine/non-polar solvent is molten;
(3) under the condition that adopts nitrogen protection, iron salt solutions is slowly splashed in the mixing solutions of amine/non-polar solvent, temperature is controlled between 20～80 ℃, and reaction continues 0.5～12 hour;
(4) adopt centrifugal method (centrifugal 10 minutes of 11000 rev/mins rotating speed) to obtain throw out after the taking-up reaction product, and with acetone and washed with de-ionized water 1～10 time, vacuum lyophilization obtained black powder after 12～24 hours, was nano ferriferrous oxide granule.
Among the present invention, Fe
3+And Fe
2+Optimum concentration is respectively 0.05～0.2mol/l and 0.025 ~ 0.1mol/l, and the mixing solutions consumption optimum of amine/non-polar solvent is 5ml/50ml, and the temperature of reaction optimum is 25 ℃～50 ℃, and the reaction times optimum is 0.5～3 hour.
Among the present invention, the optimum kind of non-polar solvent is the alkane of six～eight carbon atoms, and oil-soluble amine is the organic amine that contains six～eight carbon atoms.
The present invention adopts the oily solution of the amine be soluble in non-polar solvent to replace ammoniacal liquor or sodium hydroxide in the former chemical coprecipitation method, coprecipitation reaction carries out on water/oily interface, thereby in the advantage that the former chemical coprecipitation of reservation can prepare in a large number, can produce following two characteristics: by slowing down of velocity of diffusion speed of response is reduced, thereby obtain the particle of the distribution of thin (the about 10nm of particle diameter) than homogeneous; The product quaternary ammonium salts of reaction is adsorbed on the nano ferriferrous oxide surface, make the surface have certain electric charge, make between particle and repel mutually, thereby obtain finely disseminated particle, this particle has good dispersiveness in water and various polarity solvent, and size distribution is homogeneous comparatively, the particle diameter surface has certain electric charge, be beneficial to and wrap up polymkeric substance thereon, and have higher saturation magnetization and superparamagnetism, have very wide bio-medical prospect.
Compared with prior art, the present invention has plurality of advantages: 1. do not use any catalyzer to react at normal temperatures and pressures; 2. the reaction process flow process is simple, sets up the continous way mode of production easily, and with short production cycle; 3. can prepare the scattered ferriferrous oxide particles of high purity fine particle in a large number.
Description of drawings
Fig. 1 is the particulate transmission electron microscope observing figure of the present invention's preparation
Embodiment
Embodiment one:
Take by weighing 0.05molFeCl
36H
2O and 0.025molFeCl
24H
2O is dissolved in the 10ml water, obtains iron salt solutions, and graduated cylinder is measured the 2ml Diisopropylamine, is dissolved in the 30ml normal hexane.Adopting under the condition of nitrogen protection, the aqueous solution of molysite is slowly splashed in Diisopropylamine/hexane solution, temperature is controlled at 25 ℃, and entire reaction continues 1 hour.Adopt centrifugal method (11000 rev/mins, 10 minutes) to clean 1 time with acetone after taking out reaction product, vacuum lyophilization obtained black powder after 12 hours, was nano ferriferrous oxide granule.
Black powder employing X-ray diffraction (XRD) method that obtains can be defined as the ferriferrous oxide particles of inverse spinel structure, and its purity is very high.
Adopt the prepared particle of transmission electron microscope observing, as shown in Figure 1, visible prepared ferriferrous oxide particles is subsphaeroidal, good dispersion, and narrow particle size distribution, size is about 10 ± 5nm.
Adopt fourier transform infrared spectrometry (FTIR), x-ray photoelectron power spectrum (XPS) and surperficial zeta potential instrument to measure the nano grain surface state of preparation, can confirm, well attached to the ferroferric oxide nano granules surface of preparation, the surface has certain positive charge to the reaction product quaternary amine.
Adopt vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) (SQUID) to measure the magnetic property that obtains ferriferrous oxide particles, its saturation magnetization is about 50emu/g, coercive force is zero, magnetization change is directly proportional with absolute temperature (K) under the differing temps, thereby determines that it has superparamagnetism.
Embodiment two:
Take by weighing 0.05molFeCl
36H
2O and 0.025molFeCl
24H
2O is dissolved in the 100ml water, obtains iron salt solutions, and graduated cylinder is measured the 10ml diisobutylamine, is dissolved in the 300ml normal heptane.Under the condition that adopts nitrogen protection, diisobutylamine/n-heptane solution is slowly splashed in the aqueous solution of molysite, temperature is controlled at 50 ℃, and entire reaction continues 0.5 hour.Adopt centrifugal method (11000 rev/mins, 10 minutes) to clean 1 time with acetone after taking out reaction product, use deionized water wash again 5 times, vacuum lyophilization obtained black powder after 24 hours, was nano ferriferrous oxide granule.
Black powder employing X-ray diffraction (XRD) method that obtains can be defined as the ferriferrous oxide particles of inverse spinel structure, and its purity is very high.
Adopt the prepared particle of transmission electron microscope observing, visible prepared ferriferrous oxide particles is subsphaeroidal, good dispersion, and narrow particle size distribution, size is about 12 ± 5nm.
Adopt fourier transform infrared spectrometry (FTIR), x-ray photoelectron power spectrum (XPS) and surperficial zeta potential instrument to measure the nano grain surface state of preparation, can confirm, well attached to the ferroferric oxide nano granules surface of preparation, the surface has certain positive charge to the reaction product quaternary amine.
Adopt vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) (SQUID) to measure the magnetic property that obtains ferriferrous oxide particles, its saturation magnetization is about 58emu/g, coercive force is zero, magnetization change is directly proportional with absolute temperature (K) under the differing temps, thereby determines that it has superparamagnetism.
Embodiment three:
Take by weighing 0.2molFeCl
36H
2O and 0.1molFeCl
24H
2O is dissolved in the 100ml water, obtains iron salt solutions, and graduated cylinder is measured the 50ml Di-n-Butyl Amine, is dissolved in the 1000ml normal hexane.Under the condition that adopts nitrogen protection, Di-n-Butyl Amine/hexane solution is slowly splashed in the aqueous solution of molysite, temperature is controlled at 60 ℃, and entire reaction continues 10 hours.Adopt centrifugal method (11000 rev/mins, 10 minutes) to clean 5 times with acetone after taking out reaction product, use deionized water wash again 5 times, vacuum lyophilization obtained black powder after 18 hours, was nano ferriferrous oxide granule.
Black powder employing X-ray diffraction (XRD) method that obtains can be defined as the ferriferrous oxide particles of inverse spinel structure, and its purity is very high.
Adopt the prepared particle of transmission electron microscope observing, visible prepared ferriferrous oxide particles is subsphaeroidal, good dispersion, and narrow particle size distribution, size is about 13 ± 6nm.
Adopt fourier transform infrared spectrometry (FTIR), x-ray photoelectron power spectrum (XPS) and surperficial zeta potential instrument to measure the nano grain surface state of preparation, can confirm, well attached to the ferroferric oxide nano granules surface of preparation, the surface has certain positive charge to the reaction product quaternary amine.
Adopt vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) (SQUID) to measure the magnetic property that obtains ferriferrous oxide particles, its saturation magnetization is about 64emu/g, coercive force is zero, magnetization change is directly proportional with absolute temperature (K) under the differing temps, thereby determines that it has superparamagnetism.
Embodiment four:
Take by weighing 0.2molFeCl
36H
2O and 0.1molFeCl
24H
2O is dissolved in the 1000ml water, obtains iron salt solutions, and graduated cylinder is measured the 50ml diisobutylamine, is dissolved in the 1000ml octane.Under the condition that adopts nitrogen protection, diisobutylamine/octane solution is slowly splashed in the aqueous solution of molysite, temperature is controlled at 80 ℃, and entire reaction continues 3 hours.Adopt centrifugal method (11000 rev/mins, 10 minutes) to clean 5 times with acetone after taking out reaction product, use deionized water wash again 5 times, vacuum lyophilization obtained black powder after 18 hours, was nano ferriferrous oxide granule.
Black powder employing X-ray diffraction (XRD) method that obtains can be defined as the ferriferrous oxide particles of inverse spinel structure, and its purity is very high.
Adopt the prepared particle of transmission electron microscope observing, visible prepared ferriferrous oxide particles is subsphaeroidal, good dispersion, and narrow particle size distribution, size is about 13 ± 5nm.
Adopt fourier transform infrared spectrometry (FTIR), x-ray photoelectron power spectrum (XPS) and surperficial zeta potential instrument to measure the nano grain surface state of preparation, can confirm, well attached to the ferroferric oxide nano granules surface of preparation, the surface has certain positive charge to the reaction product quaternary amine.
Adopt vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) (SQUID) to measure the magnetic property that obtains ferriferrous oxide particles, its saturation magnetization is about 62emu/g, coercive force is zero, magnetization change is directly proportional with absolute temperature (K) under the differing temps, thereby determines that it has superparamagnetism.
Embodiment five:
Take by weighing 0.1molFeCl
36H
2O and 0.05molFeCl
24H
2O is dissolved in the 100ml water, obtains iron salt solutions, and graduated cylinder is measured the 5ml diisobutylamine, is dissolved in the 50ml octane.Under the condition that adopts nitrogen protection, diisobutylamine/octane solution is slowly splashed in the aqueous solution of molysite, temperature is controlled at 40 ℃, and entire reaction continues 5 hours.Adopt centrifugal method (11000 rev/mins, 10 minutes) to clean 5 times with acetone after taking out reaction product, use deionized water wash again 5 times, vacuum lyophilization obtained black powder after 18 hours, was nano ferriferrous oxide granule.
Black powder employing X-ray diffraction (XRD) method that obtains can be defined as the ferriferrous oxide particles of inverse spinel structure, and its purity is very high.
Adopt the prepared particle of transmission electron microscope observing, visible prepared ferriferrous oxide particles is subsphaeroidal, good dispersion, and narrow particle size distribution, size is about 14 ± 5nm.
Adopt fourier transform infrared spectrometry (FTIR), x-ray photoelectron power spectrum (XPS) and surperficial zeta potential instrument to measure the nano grain surface state of preparation, can confirm, well attached to the ferroferric oxide nano granules surface of preparation, the surface has certain positive charge to the reaction product quaternary amine.
Adopt vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) (SQUID) to measure the magnetic property that obtains ferriferrous oxide particles, its saturation magnetization is about 60emu/g, coercive force is zero, magnetization change is directly proportional with absolute temperature (K) under the differing temps, thereby determines that it has superparamagnetism.
Claims (10)
1. a method for preparing the nano ferriferrous oxide granule that dissolves in polar solvent is characterized in that, may further comprise the steps:
(1) takes by weighing FeCl
36H
2O and FeCl
24H
2O, its mol ratio is 2: 1, and is soluble in water, obtains iron salt solutions;
(2) graduated cylinder is measured oil-soluble amine, is dissolved in the non-polar solvent, and the mixing that obtains amine/non-polar solvent is molten;
(3) under the condition that adopts nitrogen protection, iron salt solutions is slowly splashed in the mixing solutions of amine/non-polar solvent, react;
(4) after the taking-up reaction product, adopt centrifugal method to obtain throw out, and, obtain black powder after the vacuum lyophilization, be nano ferriferrous oxide granule with acetone and washed with de-ionized water.
2. preparation according to claim 1 dissolves in the method for the nano ferriferrous oxide granule of polar solvent, it is characterized in that, in the step (1), takes by weighing FeCl
36H
2O and FeCl
24H
2O is dissolved in 10～1000ml water.
3. dissolve in the method for the nano ferriferrous oxide granule of polar solvent according to claim 1 or 2 described preparations, it is characterized in that Fe
3+And Fe
2+Concentration is respectively 0.05～0.2mol/l and 0.025～0.1mol/l.
4. preparation according to claim 1 dissolves in the method for the nano ferriferrous oxide granule of polar solvent, it is characterized in that, in the step (2), graduated cylinder is measured the amine that 2～50ml easily is dissolved in non-polar solvent, be dissolved in 30～1000ml non-polar solvent, the mixing that obtains amine/non-polar solvent is molten, and the mixing solutions consumption of amine/non-polar solvent is 5ml/50ml.
5. dissolve in the method for the nano ferriferrous oxide granule of polar solvent according to claim 1 or 4 described preparations, it is characterized in that non-polar solvent is the alkane of six～eight carbon atoms.
6. dissolve in the method for the nano ferriferrous oxide granule of polar solvent according to claim 1 or 4 described preparations, it is characterized in that oil-soluble amine is the organic amine that contains six～eight carbon atoms.
7. preparation according to claim 1 dissolves in the method for the nano ferriferrous oxide granule of polar solvent, it is characterized in that, in the step (3), temperature of reaction is controlled between 20～80 ℃, and the reaction times is 0.5～12 hour.
8. dissolve in the method for the nano ferriferrous oxide granule of polar solvent according to claim 1 or 7 described preparations, it is characterized in that temperature of reaction is 25 ℃～50 ℃, the reaction times is 0.5～3 hour.
9. preparation according to claim 1 dissolves in the method for the nano ferriferrous oxide granule of polar solvent, it is characterized in that, in the step (4), adopts centrifugal method to obtain throw out, is meant: adopt 11000 rev/mins rotating speed to obtain throw out in centrifugal 10 minutes.
10. dissolve in the method for the nano ferriferrous oxide granule of polar solvent according to claim 1 or 9 described preparations, it is characterized in that, in the step (4), with acetone and washed with de-ionized water 1～10 time, vacuum lyophilization 12～24 hours.
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| CN101875508B (en) * | 2010-05-31 | 2013-07-31 | 沈阳药科大学 | Preparation method of Fe3O4 nano-magnetic powder lymphatic tracer and application thereof |
| CN104649332A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for preparing superparamagnetic ferroferric oxide nanocrystal at room temperature |
| CN111961641B (en) * | 2020-07-20 | 2021-09-17 | 暨南大学 | Magnetic composite microcarrier, preparation method thereof and application thereof in cell suspension culture |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365951A (en) * | 2001-01-15 | 2002-08-28 | 中国科学院广州能源研究所 | Process for preparin dispersive nano Fe3O4 particles |
| CN1474417A (en) * | 2003-08-13 | 2004-02-11 | 武汉理工大学 | High specific saturated magnetizing strengh Fe3O4 micro particles and its preparing method |
| JP2004182526A (en) * | 2002-12-03 | 2004-07-02 | Nok Corp | Method of manufacturing magnetite fine particle |
| CN1557725A (en) * | 2004-01-13 | 2004-12-29 | 上海大学 | Method for manufacturing nano-sized Fe3O4 |
| CN1611449A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院兰州化学物理研究所 | Method for preparing Fe3 O4 superfine powder |
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2005
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365951A (en) * | 2001-01-15 | 2002-08-28 | 中国科学院广州能源研究所 | Process for preparin dispersive nano Fe3O4 particles |
| JP2004182526A (en) * | 2002-12-03 | 2004-07-02 | Nok Corp | Method of manufacturing magnetite fine particle |
| CN1474417A (en) * | 2003-08-13 | 2004-02-11 | 武汉理工大学 | High specific saturated magnetizing strengh Fe3O4 micro particles and its preparing method |
| CN1611449A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院兰州化学物理研究所 | Method for preparing Fe3 O4 superfine powder |
| CN1557725A (en) * | 2004-01-13 | 2004-12-29 | 上海大学 | Method for manufacturing nano-sized Fe3O4 |
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