CN101391818B - Synthetic method of super-paramagnetic ferriferrous oxide nano sphere - Google Patents
Synthetic method of super-paramagnetic ferriferrous oxide nano sphere Download PDFInfo
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- CN101391818B CN101391818B CN2008100720026A CN200810072002A CN101391818B CN 101391818 B CN101391818 B CN 101391818B CN 2008100720026 A CN2008100720026 A CN 2008100720026A CN 200810072002 A CN200810072002 A CN 200810072002A CN 101391818 B CN101391818 B CN 101391818B
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Abstract
The invention provides a method for synthesizing super paramagnetic ferroferric oxide nanometer spheres, and relates to a magnetic material, in particular to a method for synthesizing super paramagnetic ferroferric oxide nanometer spheres through solvent-thermal process. With simple technique, cheap and easy access to raw materials and low cost, the method for synthesizing super paramagnetic ferroferric oxide nanometer spheres can adjust and control the grain diameters of the products by easy enlargement, without adding any protecting agent. The method for synthesizing super paramagnetic ferroferric oxide nanometer spheres comprises the following steps of: preparing mixed solvent of glycol and tetrahydrofuran; dissolving malysite and urea into the mixed solvent to acquire mixed solution; moving the mixed solution into inner lining of the polyfluortetraethylene; putting the inner lining of the polyfluortetraethylene into a reaction kettle for reaction; and washing at least one time the acquired solid products by ethanol and water respectively, to obtain the ferroferric oxide nanometer spheres.
Description
Technical field
The present invention relates to a kind of magneticsubstance, especially relate to a kind of method by the synthetic super-paramagnetic ferriferrous oxide nano sphere of solvent-thermal method.
Background technology
The development of nanosecond science and technology is recognized people gradually: when the size of material reached nanoscale, regular meeting showed the character different with body phase material.And these character relevant with size also more and more are subjected to people's attention.Nano magnetic material is as a kind of emerging functional materials, because its unique physicochemical property make it show the special purpose different with conventional magneticsubstance at aspects such as physics, chemistry.Nano ferriferrous oxide is exactly wherein a kind of multifunction magnetic material, has application widely aspect magnetic recording material, magnetic fluid, medicine, pigment etc. and the catalysis.When the particle of nano ferriferrous oxide during less than critical size, will show superparamagnetism, its critical size is relevant with temperature, and spherical iron nano-particle is 12.5nm in the critical radius of room temperature.The nano ferriferrous oxide of super paramagnetic and the body difference of Z 250 maximum mutually can keep good dispersiveness down with regard to the environment that is not have externally-applied magnetic field and can not reunite, and can assemble with field direction under the effect of externally-applied magnetic field.Just be based on above characteristics, super paramagnetic nano magneticsubstance is representing good prospects for application aspect protein separation, the pharmaceutical carrier.Wherein be subjected to investigator's extensive attention because of its good character with the nanometer ball of super-paramagnetic ferriferrous oxide nano granulometric composition.
At present both at home and abroad report to main in a series of researchs of super-paramagnetic ferriferrous oxide nano sphere synthetic be to be based upon following two class methods: the one, under adding by protectant solvent thermal condition, allow reactants water separate and obtain paramagnetic ferriferrous oxide nano sphere (Angew.chem.2005,117,2842-2845); The 2nd, by solution reaction, under protectant condition, allow the hydrolysis of reactant uniform mixing post-heating, obtain super-paramagnetic ferriferrous oxide nano sphere (Angew.Chem..Int.Ed.2007,46,4342-4345).These two kinds of methods also can access relatively large product simultaneously, so receive investigator's concern always because reaction conditions is comparatively simple.These two kinds of methods also exist identical weak point, have been to obtain paramagnetic ferriferrous oxide nano sphere and a large amount of non-reactant (protective material) of needs interpolation.And these protectant prices even than reactant costliness, this just makes these methods be restricted in the application facet in chemical industry field.Developing a kind of effective and economic paramagnetic ferriferrous oxide nano sphere synthetic method is an application oriented challenge.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, raw material is cheap and easy to get, with low cost, the synthetic method that is easy to amplify, can regulates and control, not add protectant ferriferrous oxide nano sphere the particle diameter of product.
Technical scheme of the present invention is by raw material cheap and easy to get, utilizes the solvent thermal reaction of mixed solvent, directly synthetic paramagnetic ferriferrous oxide nano sphere.
The present invention includes following steps:
1) ethylene glycol and tetrahydrofuran (THF) are mixed with mixed solvent;
2) molysite and urea are dissolved in the mixed solvent of step 1) gained, get mixing solutions;
3) with step 2) mixing solutions of gained is transferred in the polytetrafluoroethyllining lining;
4) polytetrafluoroethyllining lining is placed reaction kettle for reaction;
5) solid product that will react the back gained is used ethanol and water washing respectively at least 1 time, promptly gets super-paramagnetic ferriferrous oxide nano sphere.
By volume, ethylene glycol: tetrahydrofuran (THF) is (1～10): 1, and be preferably ethylene glycol: tetrahydrofuran (THF) is (1～6): 1, molysite can be selected from nine nitric hydrate iron or six Ferric Chloride Hydrateds etc.; In molar ratio, molysite: urea is 1: (2～4) are preferably molysite: urea is 1: 2.
The temperature of reaction is 180～250 ℃, and the time of reaction is 8h at least, and preferably Fan Ying temperature is 180 ℃, and the time of reaction is 12h.
The present invention passes through solvent-thermal method, utilize the urea decomposes to promote the hydrolysis of molysite, simultaneously with the mixed solvent of ethylene glycol and tetrahydrofuran (THF) as disperse phase and reductive agent, system just can the spontaneous super-paramagnetic ferriferrous oxide nano sphere that obtains high yield, favorable dispersity under the temperature and pressure of solvent thermal condition.Compare with other the synthetic method of super-paramagnetic ferriferrous oxide nano sphere, the present invention has the following advantages: 1) the present invention is not owing to need to add any stablizer, utilize the system self of simple inorganic salt hydrolysis just can form super-paramagnetic ferriferrous oxide nano sphere, therefore needed raw material is all very cheap, the required cost of entire reaction is low, can be described as similar other method can not compare.2) preparation method of traditional super-paramagnetic ferriferrous oxide nano sphere is because need to add stablizer, so more or less increased the postprocessing working procedures complicacy; And the present invention need not to add stablizer, so aftertreatment is simple.3) can prepare the narrower super-paramagnetic ferriferrous oxide nano sphere of size distribution by the present invention, and can regulate and control its particle diameter.4) the solvent thermal synthesis method of the present invention's introducing, its synthesizer is simple, and is workable, the preparation process mild condition, the reaction process cleanliness without any pollution, the reaction efficiency height has very high industrial synthetic prospect.
Description of drawings
Fig. 1 is the product low power SEM figure of the embodiment of the invention 1 prepared super-paramagnetic ferriferrous oxide nano sphere.
Fig. 2 is the product high power SEM figure of the embodiment of the invention 1 prepared super-paramagnetic ferriferrous oxide nano sphere.
Fig. 3 is the product low power TEM figure of the embodiment of the invention 1 prepared super-paramagnetic ferriferrous oxide nano sphere.In Fig. 3, scale is 200nm.
Fig. 4 is the product high power TEM figure of the embodiment of the invention 1 prepared super-paramagnetic ferriferrous oxide nano sphere.In Fig. 4, scale is 50nm.
Fig. 5 is the XRD figure of the product of the embodiment of the invention 1 prepared super-paramagnetic ferriferrous oxide nano sphere.In Fig. 5, X-coordinate is peak position Position (2 θ/°), and ordinate zou is intensity I ntensity (a.u.).
Fig. 6 is the product S EM figure of the embodiment of the invention 2 prepared super-paramagnetic ferriferrous oxide nano spheres.
Fig. 7 is the product TEM figure of the embodiment of the invention 2 prepared super-paramagnetic ferriferrous oxide nano spheres.In Fig. 7, scale is 200nm.
Fig. 8 is the product S EM figure of the embodiment of the invention 3 prepared super-paramagnetic ferriferrous oxide nano spheres.
Fig. 9 is the product TEM figure of the embodiment of the invention 3 prepared super-paramagnetic ferriferrous oxide nano spheres.In Fig. 9, scale is 200nm.
Figure 10 is the product S EM figure of the embodiment of the invention 4 prepared super-paramagnetic ferriferrous oxide nano spheres.
Figure 11 is the product TEM figure of the embodiment of the invention 4 prepared super-paramagnetic ferriferrous oxide nano spheres.In Figure 11, scale is 100nm.
Figure 12 is the product S EM figure of the embodiment of the invention 5 prepared super-paramagnetic ferriferrous oxide nano spheres.
Figure 13 is the product TEM figure of the embodiment of the invention 5 prepared super-paramagnetic ferriferrous oxide nano spheres.In Figure 13, scale is 100nm.
Figure 14 is the product S EM figure of the embodiment of the invention 6 prepared super-paramagnetic ferriferrous oxide nano spheres.
Figure 15 is the product TEM figure of the embodiment of the invention 6 prepared super-paramagnetic ferriferrous oxide nano spheres.
In Fig. 1～15, SEM figure is a sem photograph, and TEM figure is a transmission electron microscope picture.
Embodiment
The invention will be further described in conjunction with the accompanying drawings below by embodiment.
Embodiment 1
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 1: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
By the product output of gained is big and pattern is single as can be seen among Fig. 1, Fig. 2 as can be seen the particle diameter major part of product about 200nm.Fig. 3 nanometer ball as can be seen is solid and dispersed better, and these nanometer balls are to be assembled at the small-particle of 10 nanometers by particle diameter to form as can be seen from Figure 4 simultaneously, and this Z 250 in this particle size range is to present superparamagnetism.From the outward appearance of products therefrom and XRD figure (referring to Fig. 5) as can be seen products therefrom be Z 250, calculate that according to XRD the small-particle particle diameter of forming microballoon is 9.3nm simultaneously, this also is consistent with the result of TEM.The action of a magnetic field through the external world flocks together Fig. 4 in the water for product is dispersed in, and when not adding foreign field product in water by good dispersiveness, can keep not reuniting for a long time.
Embodiment 2
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 2: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
By Fig. 6 and 7 as can be seen the product pattern of gained good unicity is arranged, dispersed better, the particle diameter major part is about 200nm.
Embodiment 3
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
By Fig. 8 and 9 as can be seen the product pattern of gained good unicity is arranged, dispersed better, the particle diameter major part is about 200nm.
Embodiment 4
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 6: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
By Figure 10 and 11 as can be seen the product pattern of gained good unicity is arranged, dispersed better, the particle diameter major part is about 200nm.
Embodiment 5
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 808mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
By Figure 12 and 13 as can be seen the product pattern of gained good unicity is arranged, dispersed better, the particle diameter major part is about 100nm.
Embodiment 6
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 16h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
By Figure 14 and 15 as can be seen the product pattern of gained good unicity is arranged, dispersed better, the particle diameter major part is about 400nm.
Embodiment 7
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 808mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 8
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 6: 1.
2) 808mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 9
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 8h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 10
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 2: 1.
2) 808mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 11
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 20h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 12
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 10: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 13
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 1: 1.
2) 808mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 16h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 14
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 6: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 20h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 15
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 270mg six Ferric Chloride Hydrateds and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 16
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 6: 1.
2) 270mg six Ferric Chloride Hydrateds and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 180 ℃ of following constant temperature 20h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out,, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 17
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 200 ℃ of following constant temperature 12h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Embodiment 18
1) preparation 15ml volume ratio is ethylene glycol/tetrahydrofuran solution of 4: 1.
2) 404mg nine nitric hydrate iron and 120mg urea are dissolved in the solution of step 1).
3) with step 2) to be transferred to volume be in the middle of the 18ml polytetrafluoroethyllining lining to gained solution.
4) polytetrafluoroethyllining lining is placed reactor, at 250 ℃ of following constant temperature 8h.
5) be cooled to and polytetrafluoroethyllining lining taken out solution after the room temperature and pour out, the gained solid product is used ethanol successively, and water respectively washs 2 times, promptly gets target product.
Claims (5)
1. the synthetic method of super-paramagnetic ferriferrous oxide nano sphere is characterized in that may further comprise the steps:
1) ethylene glycol and tetrahydrofuran (THF) are mixed with mixed solvent, by volume, ethylene glycol: tetrahydrofuran (THF) is 1～10: 1;
2) molysite and urea are dissolved in the mixed solvent of step 1) gained, get mixing solutions, in molar ratio, molysite: urea is 1: 2～4;
3) with step 2) mixing solutions of gained is transferred in the polytetrafluoroethyllining lining;
4) polytetrafluoroethyllining lining is placed reaction kettle for reaction, the temperature of described reaction is 180～250 ℃, and the time of reaction is 8h at least;
5) solid product that will react the back gained is used ethanol and water washing respectively at least 1 time, promptly gets super-paramagnetic ferriferrous oxide nano sphere.
2. the synthetic method of super-paramagnetic ferriferrous oxide nano sphere as claimed in claim 1, it is characterized in that by volume ethylene glycol: tetrahydrofuran (THF) is 1～6: 1.
3. the synthetic method of super-paramagnetic ferriferrous oxide nano sphere as claimed in claim 1 is characterized in that molysite is nine nitric hydrate iron or six Ferric Chloride Hydrateds.
4. the synthetic method of super-paramagnetic ferriferrous oxide nano sphere as claimed in claim 1, it is characterized in that in molar ratio molysite: urea is 1: 2.
5. the synthetic method of super-paramagnetic ferriferrous oxide nano sphere as claimed in claim 1 is characterized in that the temperature of reacting is 180 ℃, and the time of reaction is 12h.
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| CN101913852A (en) * | 2010-07-17 | 2010-12-15 | 厦门大学 | Method for synthesizing spherical superparamagnetic ferrite nano druse |
| CN102153149B (en) * | 2010-12-29 | 2012-10-24 | 济南大学 | Method for preparing nano quantum dot level Fe3O4 superparamagnetic particles |
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