CN101712011B - Method for centrifugally separating oil soluble nano particles by organic density gradient - Google Patents
Method for centrifugally separating oil soluble nano particles by organic density gradient Download PDFInfo
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Abstract
The invention relates to a method for centrifugally separating oil soluble nano particles by organic density gradient. The method comprises the following steps: 1) directly synthesizing nano particle colloidal solution, or carrying out ultrasonic and stirring and other methods on the nano particles in organic solvent to prepare colloidal nano particle solution with transparent homogeneity; 2) preparing organic density gradient medium by mixing organic solvent or high-molecular solution with different densities; 3) adding organic density gradient medium with different concentrations to a centrifuge tube in turn to prepare organic density gradient; and 4) adding the colloidal solution of nano particles into the organic density gradient for centrifuging. As the sedimentation rate of the nano particles with different sizes and appearances in the organic density gradient solution is different, the nano particles are retained at different positions of the organic density gradient solution, thus achieving the effect of separation. The invention has the advantage of volatilizing the organic solvent to obtain the monodisperse nano particles; the method of the invention is simple and rapid, is influenced little by the stability and purity of the sample, and the centrifuging effect can be strengthened by adjusting the centrifugal parameter.
Description
Technical field
The present invention relates to the method for a kind of separating oil soluble oil dissolubility noble metal and semi-conductor nano particles, particularly a kind of method of organic density gradient high speed centrifugation separation oil-soluble nano particles belongs to advanced nano material separation process technique field.
Background technology
Nano material produces physics, the chemical characteristic of aspects such as special light, electricity, heat because its dimensional effect makes its physical and chemical performance compare with common material and has very big difference.The performance that nano material is so excellent has significant relationship with its size, so the acquisition of the single nano particle of size has significant meaning to application and the development of nano material.
Present stage, though the nano material synthetic method is a lot, have in addition can synthesize the single mono-dispersed nano particle of size, all be the synthesis condition harshness often, equipment is had relatively high expectations.Another kind method is to obtain the mono-dispersed nano particle by separating.The separation method that present stage is applied to the nanometer field mainly contain centrifugal (Anal.Chem.2001,73,5758-5761), " anti-solvent " selective precipitation method (Adv.Mater.2007,19,548-552; Nano.Lett.2005,5,461-465), electrophoresis (Chem.Commun.2005,787-788), chromatography (Langmuir.1989,5,429-432; Nano.Lett.2007,7,2881-2885), filtration method (Adv.Mater.2005,17,532-535), dialysis (J.Am.Chem.Soc.2006,128,3190-3197) etc.Though these methods have all obtained certain achievement, also come with some shortcomings, such as separating not exclusively, efficient is low, needs special equipment etc.Other separation means, as utilize magnetic field to separate this journey nano particle, relative efficiency is higher, but can not be used for other nanometers separation (Science.2006,314,964-967).Density gradient high speed centrifugation speed is separated is a kind of separation method of pure liquid phase, has avoided loss that colloidal particle and the collision that separates phase cause and the destruction of product structure, is a kind of very potential separation method.But, this method is former before this for separation (the Centrifugation in Density Gradients.1982.Academic Press of large biological molecule, ISBN:0125645805) grow up, therefore range of application only limits to aqueous phase system (J.AM.CHEM.SOC.2008,130,6551-6555; Agew.Chem.In.Ed.2008.47).But for nano material, have many nano materials all synthetic at oil phase, finally the form with the oil-soluble colloidal particle exists.Whether we can select two kinds of organic solvents that density is different so, mix with different ratios, made into the separation that density gradient is carried out oil-soluble nano particles then? at present, the example that separates in organic phase is not seen in report as yet.What the use organic phase was separated is also advantageous in that the organic solvent of selecting for us is a lot, after having separated, only organic solvent need be volatilized, and we just can be easy to obtain the mono-dispersed nano material, have significantly reduced the purifying cost.So in organic phase, separate with the density gradient supercentrifugal process, the application of nano material had bright prospects and great scientific meaning.This provides the basis for the performance of further studying nano material, also will further illustrate the dependence of function nano scantling and structure, for fields such as novel photoelectric material, nano-device provide abundant material foundation, be a job highly significant, application and the development of nano material had significant meaning.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts organic density gradient method to separate the oil-soluble nano particles of different sizes.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of organic density gradient separation oil-soluble nano particles is characterized in that the concrete steps of this method are:
A. will be ultrasonic by the oil-soluble nano particles colloidal solution of chemical method preparation, being mixed with the quality volumetric concentration is the nanometer particle colloid solution of 0.01-50mg/ml;
B. compound concentration difference (being that density is descending) successively, and can make organic density gradient medium solution of oil-soluble nano particles stable existence is got isopyknic medium solution successively by the order from the high concentration to the low concentration and is added centrifuge tube and be mixed with gradient solution;
C. a certain amount of step a gained solution is placed on the gradient solution of step b gained;
D. be 4-25 ℃ in temperature, rotating speed is 5000-65000 rev/min, and the time is high speed centrifugation under 5-480 minute the condition, obtains a kind of nanoparticle dispersion liquid according to the nano particle size distribution;
E. the nanoparticle dispersion liquid after centrifugal is taken out by the top in batches; Finally obtain the monodisperse nanoparticle dispersed liquid component of different sizes and pattern.
The density of used nano particle will be higher than organic density gradient solution density of medium in the technique scheme.
For separating of nano particle be metal nanoparticle, oxide nano-particles, magnetic nano-particle, nano heterogeneous joint structure or semi-conductor nano particles.
The described medium solution for the organic density gradient solution of preparation of technical scheme steps b adopts cyclohexane, carbon tetrachloride, benzene, toluene, chloroform, pentane, ethanol, ethylene glycol etc. variant with the nanometer particle colloid solution density, and the mixture of selecting wantonly two components or multiple mutual mixing to form in the organic solvent that dissolves each other; Or be dissolved with the mixture of high molecular organic solution and mixable organic solvent.
The size range of the described nano particle of technical scheme steps a is from 1 nanometer to 2 micron.
After technical scheme steps e finished, repeating step b-e carried out secondary even separating for several times, to optimize the Size Distribution of nano particle.
The present invention compared with prior art has the following advantages and the high-lighting effect: 1. good separating effect can once obtain than the pure sample product; 2. the size of separation scope is wide, from the nanometer to the micrometer range; 3. this method both can be separated according to size, can separate according to difference in functionality again; 4. realize different separation purposes by regulating parameter of noncentricity; 5. this method is a kind of harmless separation method of pure liquid phase.6. purifying is simple, only organic solvent need be volatilized, and just can be easy to obtain the mono-dispersed nano particle.
Description of drawings
Fig. 1 is the digital photograph of the centrifugal front and back of the embodiment of the invention one Au nano particle centrifuge tube.
Fig. 2 is that the TEM picture A-E of the different numbers of plies is respectively the the the 3rd, the 6th, the 9th, the 12nd, the 15th layer TEM photo after the embodiment of the invention one Au nano particle centrifugation.F is the variation diagram that its average-size increases with component.
Fig. 3 is that the TEM picture A-C of the different numbers of plies is respectively the the 3rd, the 5th, the 9th layer TEM photo after the embodiment of the invention two Au nano wire/nano particle centrifugation.
Fig. 4 is different number of plies Fe after the embodiment of the invention three centrifugations
3O
4TEM picture A-the C of nano particle is respectively the 3rd, the 7th, the TEM photo of 11th layer.。
Fig. 5 is that the TEM picture A-E of the different numbers of plies in the centrifugal back of the embodiment of the invention four CdSe nano particles is respectively the the the 5th, the 7th, the 10th, the 13rd, the 16th layer TEM photo.F is the variation diagram that its average-size increases with component.
Fig. 6 is the embodiment of the invention four Cdse nano particles after adding polystyrene and improving the viscosity gradient fluid viscosity, and the fluorescence spectrum figure of the different numbers of plies after the centrifugation---the variation that has shown its size is moved in the position at CdSe fluorescence spectrum peak.
The specific embodiment
Embodiment one:
(1) at first, use the HAuCl of 10mg/ml
480 ℃ of oleyl amine solution and 10ml cyclohexanes, 10h reaction, the cyclohexane colloidal solution of the Au nano particle of the about 1mg/ml of generation.
(2) make density gradient: the cyclohexane solution that is mixed with percent by volume 50%, 60%, 70%, 80%, 90% carbon tetrachloride with carbon tetrachloride and cyclohexane.Since 90%, the solution of getting 2ml successively adds centrifuge tube gently, is mixed with gradient solution.
(3) the cyclohexane dispersion liquid with the 0.4mlAu nano particle is added on the gradient liquid.
(4) 15 ℃, 100 * 10
-6Atmospheric pressure, 25000rpm, high speed centrifugation under the 10min condition.
(5) mixed liquor after centrifugal is divided into 16 parts, with liquid-transfering gun from the top sucking-off.Finally obtain the different Au nanoparticle dispersion liquid of size.
Separating resulting is referring to Fig. 1, and 2.
Change separation condition, change density gradient into 20%, 30%, 40%, 50%, 60%, centrifugal condition changes 15 ℃ into, and 100 * 10
-6Atmospheric pressure, 20000rpm, 8min can get similar separating effect; Equally doing density gradient medium with toluene and carbon tetrachloride, benzene and carbon tetrachloride, pentane and carbon tetrachloride or cyclohexane and chloroform separates also and can obtain similar effect.
Embodiment two:
(1) at first, use the HAuCl of 10mg/ml
450 ℃ of oleyl amine solution 5ml and 5ml cyclohexanes, 72h reaction, the colloidal solution of Au nano wire/nano particle of the about 5mg/ml of generation.
(2) preparation density gradient: the cyclohexane solution that is mixed with percent by volume 50%, 60%, 70%, 80%, 90% carbon tetrachloride with carbon tetrachloride and cyclohexane.Since 90%, the solution of getting 2ml successively adds centrifuge tube gently, is mixed with gradient solution.
(3) 0.4ml is synthetic Au nano wire/nanometer particle colloid solution is added on the gradient liquid.
(4) 15 ℃, 100 * 10
-6Atmospheric pressure, 30000rpm, high speed centrifugation under the 18min condition.
(5) mixed liquor after centrifugal is divided into 26 parts, with liquid-transfering gun from the top sucking-off.Finally obtain size, the different nanoparticle dispersion liquid of pattern.
Separating resulting is referring to Fig. 3
Change separation condition, change density gradient into 20%, 30%, 40%, 50%, 60%, centrifugal condition changes 15 ℃ into, and 100 * 10
-6Atmospheric pressure, 30000rpm, 10min can get similar separating effect; Equally doing density gradient medium with toluene and carbon tetrachloride, benzene and carbon tetrachloride, pentane and carbon tetrachloride or cyclohexane and chloroform separates also and can obtain similar effect.
Embodiment three:
(1) at first, get the Fe of 2ml oleic acid parcel
3O
4The cyclohexane colloidal solution of nano particle ultrasonic 4 hours, changes water per half an hour one time.
(2) make density gradient: the cyclohexane solution that is mixed with percent by volume 50%, 60%, 70%, 80%, 90% carbon tetrachloride with carbon tetrachloride and cyclohexane.Since 90%, the solution of getting 2ml successively adds centrifuge tube gently, is mixed with gradient solution.
(3) with the Fe of 0.4ml
3O
4The colloidal solution of nano particle is added on the gradient liquid.
(4) 15 ℃, 100 * 10
-6Atmospheric pressure, 35000rpm, high speed centrifugation under the 35min condition.
(5) mixed liquor after centrifugal is divided into 20 parts, with liquid-transfering gun from the top sucking-off.Finally obtain the different Fe of size
3O
4Nanoparticle dispersion liquid.
Separating resulting is referring to Fig. 4
Change separation condition, change density gradient into 20%, 30%, 40%, 50%, 60%, centrifugal condition changes 15 ℃ into, and 100 * 10
-6Atmospheric pressure, 35000rpm, 20min can get similar separating effect; Equally doing density gradient medium with toluene and carbon tetrachloride, benzene and carbon tetrachloride, pentane and carbon tetrachloride or cyclohexane and chloroform separates also and can obtain similar effect.
Embodiment four:
(1) at first, get 0.1mmolSeO
2Add in the there-necked flask of 6.3ml octadecylene 240 ℃ of reactions after 3 minutes with the cadmium stearate of 0.1mmol, add 1ml oleic acid with the 10 seconds/speed of dripping, continue to obtain CdSe nanometer particle colloid solution at 240 ℃ of reaction 1h.
(2) make density gradient: the cyclohexane solution that is mixed with percent by volume 40%, 50%, 60%, 70%, 80% carbon tetrachloride with carbon tetrachloride and toluene.Since 80%, the solution of getting 0.6ml successively adds centrifuge tube gently, is mixed with gradient solution.
(3) 0.4mlCdSe colloidal solution is added on the gradient liquid.
(4) 15 ℃, 100 * 10
-6Atmospheric pressure, 50000rpm, high speed centrifugation under the 55min condition.
(5) mixed liquor after centrifugal is divided into 17 parts, with liquid-transfering gun from the top sucking-off.Finally obtain the different CdSe nanoparticle dispersion liquid of size.
Separating resulting is referring to Fig. 5.
Change separation condition, change density gradient into 20%, 30%, 40%, 50%, 60%, centrifugal condition changes 15 ℃ into, and 100 * 10
-6Atmospheric pressure, 50000rpm, 30min can get similar separating effect; Equally doing density gradient medium with toluene and carbon tetrachloride, benzene and carbon tetrachloride, pentane and carbon tetrachloride or cyclohexane and chloroform separates also and can obtain similar effect.
Embodiment five:
(1) at first, use CCl
4Be mixed with the polystyrene CCl that concentration is 0.03g/ml with polystyrene sphere
4Solution.
(2) make density gradient: be mixed with percent by volume 40%, 50%, 60%, 70%, 80% solution with above-mentioned solution and toluene.Since 80%, the solution of getting 0.6ml successively adds centrifuge tube gently, is mixed with gradient solution.
(3) colloidal solution with the CdSe nano particle among the embodiment four of 0.4ml is added on the gradient liquid.
(4) 15 ℃, 100 * 10
-6Atmospheric pressure, 50000rpm, high speed centrifugation under the 110min condition.
(5) mixed liquor after centrifugal is divided into 17 parts, with liquid-transfering gun from the top sucking-off.Finally obtain the different CdSe nanoparticle dispersion liquid of size.
Separate the fluorogram of each component of back referring to Fig. 6.
Change separation condition, change density gradient into 20%, 30%, 40%, 50%, 60%, centrifugal condition changes 15 ℃ into, and 100 * 10
-6Atmospheric pressure, 50000rpm, 50min can get similar separating effect; Equally doing density gradient medium with toluene and carbon tetrachloride, benzene and carbon tetrachloride, pentane and carbon tetrachloride or cyclohexane and chloroform separates also and can obtain similar effect.
Claims (5)
1. method that organic density gradient high speed centrifugation separates oil-soluble nano particles is characterized in that this method carries out as follows:
A. nano particle is mixed with the nanometer particle colloid solution that the quality volumetric concentration is 1-50mg/ml in organic solvent;
B. compound concentration difference, and can make oil-soluble nano particles keep organic density gradient medium solution of stable colloid state, get required solution successively by the order from the high concentration to the low concentration and add centrifuge tube, be mixed with gradient solution; The described organic density gradient medium solution of step b adopts with the nanometer particle colloid solution density variant, and select the mixture of wantonly two components or multiple mutual mixing formation in the organic solvent that dissolves each other, or be dissolved with the mixture of high molecular organic solution and mixable organic solvent; The density of nanometer particle colloid solution will be higher than the density of organic density gradient medium solution;
C. step a gained nanometer particle colloid solution is placed on the gradient media solution of step b gained;
D. be 4-25 ℃ in temperature, rotating speed is 25000-65000 rev/min, and the time is centrifugal under 5-480 minute the condition, obtains a kind of nanoparticle dispersion liquid according to the nano particle size distribution;
E. the nanoparticle dispersion liquid after centrifugal is taken out by the top in batches, obtain the monodisperse nanoparticle dispersed liquid component of different sizes and pattern.
2. organic density gradient high speed centrifugation according to claim 1 separates the method for oil-soluble nano particles, it is characterized in that: become nanometer particle colloid solution among the step a, be with nano particle by the ultrasonic colloidal solution that reaches transparent and homogeneous, or the direct synthetic homogeneous nanometer particle colloid solution that forms.
3. organic density gradient high speed centrifugation according to claim 1 separates the method for oil-soluble nano particles, and it is characterized in that: the described nano particle of step a is metal nanoparticle, oxide nano-particles, magnetic nano-particle, nano heterogeneous joint structure or semi-conductor nano particles.
4. organic density gradient high speed centrifugation according to claim 1 separates the method for oil-soluble nano particles, it is characterized in that: the size range of the described nano particle of step a is from 1 nanometer to 2 micron.
5. organic density gradient high speed centrifugation according to claim 1 separates the method for oil-soluble nano particles, and after step e finished, repeating step b-e carried out that secondary is above to be separated.
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| CN102614975A (en) * | 2012-04-06 | 2012-08-01 | 东南大学 | Method used for selectively separating water-soluble nanometer particles |
| CN103723678B (en) * | 2013-12-23 | 2017-02-15 | 北京化工大学 | Method for switching media for nano-particles or separating same from one another according to sizes and/or shapes of nano-particles |
| CN105233968B (en) * | 2015-06-17 | 2017-11-14 | 陶栋梁 | A kind of method for separating different-grain diameter nano-particle |
| CN106040589B (en) * | 2016-07-11 | 2018-08-31 | 阜阳师范学院 | A method of separation different-grain diameter nanometer aluminium powder |
| CN110026298A (en) * | 2019-04-18 | 2019-07-19 | 哈尔滨工业大学 | A kind of micro-nano powder partial size centrifugal classification apparatus and its application method |
| CN110605384A (en) * | 2019-10-16 | 2019-12-24 | 成都理工大学 | Method for separating single-size indium nanocubes by using onion extract |
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| CN101171372A (en) * | 2005-03-04 | 2008-04-30 | 西北大学 | Separation method of carbon nanotubes in density gradients |
| CN101306808A (en) * | 2008-07-01 | 2008-11-19 | 上海大学 | Centrifugal separation process of carbon nano-tubes by density gradient method |
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| CN101171372A (en) * | 2005-03-04 | 2008-04-30 | 西北大学 | Separation method of carbon nanotubes in density gradients |
| CN101306808A (en) * | 2008-07-01 | 2008-11-19 | 上海大学 | Centrifugal separation process of carbon nano-tubes by density gradient method |
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