CN1229305C - Method for preparing ferrite/silicon dioxide core-shell nano particles by using ultrasonic treatment - Google Patents
Method for preparing ferrite/silicon dioxide core-shell nano particles by using ultrasonic treatment Download PDFInfo
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Abstract
The present invention relates to a method for preparing ferrite-silicone dioxide nuclear shell nanometer particles by ultrasonic processing, which belongs to the field of magnetic nanometer materials. The method comprises the steps: ferrite nanometer particles are firstly prepared by a coprecipitation method; then the ultrasonic processing of the ferrite nanometer particles is carried out; the ferrite nanometer particles are coated twice by an inorganic silicon resource and an organic silicon source. The particle diameter of the prepared nuclear shell nanometer particles is about 50 to 200 NM, and the ferrite nanometer particles in each particle are about 10 to 50. The ultrasonic processing comprises the steps: the ferrite nanometer particles are prepared into water solution having the concentration of 0.25 to 10 G/L, and the water solution is processed for 5 to 60 minutes in ultrasonic waves having the frequency of 20 to 80kHz. The reaction concentration of the ferrite nanometer particles is high in the two coating processes. The method can synthesize nuclear shell nanometer particles having multiple nuclear number, strong magnetism and small dimension and magnetic particles having good chemical stability, strong antioxidant capability and no denudation, and the particles are further functionalized, and furthermore, the method can be used for the field of biologic materials, sealing materials, magnetic recording materials, etc.
Description
Technical field
The invention belongs to the magnetic Nano material field, particularly a kind of preparation method of core-shell type magnetic nano particle.
Background technology
Ferrite nano particles is widely used at aspects such as sealing, lubricated, printing and magnetic recordings.Recently, ferrite nano particles also comes into one's own with biological relevant field day by day at some, as nuclear magnetic resonance, bioseparation, drug conveying and treatment.But, owing to there is stronger magnetic dipole effect easily to form big aggregate between the ferrite nano particles, add that particle can dissolving under acidic conditions and it is greatly limited in use.For this reason, ferrite nano particles generally all will coat before use, realizes dispersion of particles and particle is played a protective role by coating layer.Coating layer now commonly used is the organic decoration layer that is made of the surface-active organic molecule of some tools, the dispersion that charge repulsion that the organic molecule by the surface produces or empty resistance effect can realize ferrite nano particles.But because these organic molecules generally are connected by non covalent bond with ferrite nano particles, the effect between the two is not strong, so the organic molecule of coating comes off and loses the dispersion of particles effect through regular meeting.In addition, the biocompatibility of the ferrite nano particles that this organic molecular species coats is relatively poor, and just having limited it greatly relates in particular to the application in field in the organism aspect biological for this.Utilize inorganic silicon-dioxide to coat ferrite nano particles and receive increasing concern, this is because the surface coating layer that silicon-dioxide forms is except can disperseing particle well, the advantage that also organic coating layer does not possess: (1) silicon-dioxide can form successive layers on the ferrite nano particles surface, thereby coming off of coating layer can not occur; (2) silicon-dioxide has good chemical stability, and ferrite nano particles is had good provide protection as oxidation rate of slowing down some easy oxidic particles and the capacity antacid that improves particle; (3) ferrite that forms after the coated with silica-silica core core/shell nanoparticles possesses excellent biological compatibility; (4) by different silylating reagents can be on silica sphere be modified various organo-functional groups, the particle after modified can combine with various biomaterials.
At present, ferrite nano particles is carried out the most frequently used technology of coated with silica, it is one piece of document that Albert P.Philipse delivers, exercise question is that " Magnetic Silica Dispersons:Preparation and Stabilityof Surface-Modified Silica Particles with a Magnetic Core " (Langmuir 1994,10,92～99), document discloses a kind of to Fe
3O
4Carry out the method for coated with silica.This method has the following steps: the preparation magnetic Fe
3O
4Nanoparticle---handle---coating of inorganic silicon source---organosilicon source and coat by surperficial peptization.Said preparation magnetic Fe
3O
4Nanoparticle is to adopt known coprecipitation method.Said surperficial peptization is handled and is to use Tetramethylammonium hydroxide to make peptizing agent, to magnetic Fe
3O
4Nanoparticle carries out peptization to be handled.It is with Na that said inorganic silicon source coats
2SiO
3Do the silicon source, the magnetic Fe after peptization is handled
3O
4Nanoparticle is put into Na
2SiO
3Fully stir in the aqueous solution, form SiO
2Coat Fe
3O
4Nanoparticle, the about 1nm of the thickness of coating layer.When the inorganic silicon source coats, Fe
3O
4The concentration of nanoparticle is 1.18g/L, SiO
2Concentration be 0.9g/L, the pH value of reaction soln is 10, stirring reaction 2 hours.It is to do the silicon source with tetraethoxy that said organosilicon source coats, and is solvent with ethanol, and the strong aqua that with the mass percent concentration is 25-28% is that catalyzer adds the magnetic Fe that coats through the inorganic silicon source
3O
4Stir behind the nanoparticle, prepare the Fe of coated with silica
3O
4-silica core core/shell nanoparticles.When the organosilicon source coats, the Fe that coats through the inorganic silicon source
3O
4The concentration of nanoparticle is about 0.011g/L.The Fe that synthesizes according to above method
3O
4-silica core core/shell nanoparticles is that its kernel is the magnetic Fe with superparamagnetism
3O
4Nanoparticle, skin are silicon-dioxide, have 6 or be less than 6 magnetic Fe in the coated with silica layer
3O
4Nanoparticle.
This technology can be very easy at Fe
3O
4Coat inorganic silicon-dioxide on the surface, formed Fe
3O
4-silica core core/shell nanoparticles has excellent biological compatibility and better chemical stability, and can carry out various finishinges by different silylating reagents, and the particulate after modified can combine with various biomaterials.But because this Fe
3O
4The magnetic Fe that coats in each particle of-silica core core/shell nanoparticles
3O
4Nanoparticle has only 6 or be less than 6, the magnetic kernel number very little, the content of magnetic substance is too low, particle magnetic a little less than, thereby limited the application of this magnetic particle.This technology synthetic Fe
3O
4The few major cause of magnetic kernel number of-silica core core/shell nanoparticles be this technology before carrying out coated with silica with peptizing agent to Fe
3O
4Particle has carried out the peptization processing, the Fe of peptization
3O
4Particle has more surface charge, and stronger electrostatic repulsion is arranged between particle, thereby can only form the less Fe of check figure after coating
3O
4-silica core core/shell nanoparticles.
(application number 03111351.6 in the patent that we have applied for, April 1 2003 applying date), we use and carry out ferrite-silica core-shell particulate that coated with silica has obtained having coenocytism without any surface-treated ferrite nano particles, this particulate magnetic substance content height has very strong magnetic.The used ferrite nano particles of this method is without any surface treatment, the ferrite nano particles interphase interaction very strong thereby coat after can form a lot of ferrite of check figure-silica core-shell particulate, but the size of this core-shell particle is bigger, generally all more than 200nm, be difficult to satisfy the needs that ask for something uses the application of small size particles.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art exactly, the method that a kind of supersound process prepares ferrite-silica core core/shell nanoparticles is proposed, can prepare the ferrite that check figure is more and size is less-silica core core/shell nanoparticles, make the ferrite particle number that is coated in each ferrite-silica core core/shell nanoparticles 10～50 scopes, keep the core-shell nano of background technology that excellent biological compatibility and better chemical stability are arranged, particulate after modified can with various biomaterial bonded advantages, have stronger magnetic and smaller size smaller simultaneously, satisfy application request.
---the technological process that surface treatment---coating of inorganic silicon source---organosilicon source coats that supersound process of the present invention prepares the method for ferrite-silica core core/shell nanoparticles, and the preparation ferrite nano particles is arranged; Said preparation ferrite nano particles is to prepare ferrite nano particles with coprecipitation method; Said surface treatment is that ferrite nano particles is done supersound process; It is ferrite nano particles to be added in contain SiO that said inorganic silicon source coats
2The aqueous solution of water-soluble inorganic salt in stir; Said organosilicon source coats, and the ferrite nano particles of finishing the coating of inorganic silicon source is distributed in the mixed solvent of alcohol and water, under the ammonification water condition, is undertaken by teos hydrolysis and condensation reaction.That is:
At first utilize known coprecipitation method to prepare ferrite nano particles, the particle diameter of the ferrite nano particles that makes is 3～12nm, utilizes tilt-pour process to separate under permanent magnetic field, and removes impurity with the pure water cleaning;
Said ultrasonic surface treatment is, washed ferrite nano particles is made into the aqueous solution of 0.25～10g/L, is supersound process 5～60 minutes in 20～80kHz ultrasonic wave in frequency;
Add again after the supersound process and contain SiO
2The aqueous solution of water-soluble inorganic salt in stir and carry out the coated with silica first time, be coated on the ferrite nano particles surface through current inorganic silicon source and form the thick silicon dioxide layer of about 2nm, utilize the magnetic separator column that the ferrite nano particles that the inorganic silicon source coats is separated again, and remove impurity with the pure water cleaning;
The ferrite nano particles of coated with silica is distributed in the mixed solvent of alcohol and water with finishing for the first time, under the ammonification water condition, carries out the coated with silica second time by teos hydrolysis and condensation reaction.
The ferrite of indication of the present invention-silica core core/shell nanoparticles, its kernel are the ferrite nano particles of coated with silica, and shell is a silicon-dioxide.Said ferrite nano particles refers to Fe
3O
4Nanoparticle, γ-Fe
2O
3Nanoparticle or mix transition metal and the magnetic ferrite nanoparticle of compound, they have superparamagnetism, and particle diameter is 3～12nm.
In aforesaid cladding process process, processing condition are to need control.Processing condition are preferably: when the inorganic silicon source coated, the concentration of magnetic ferrite nanoparticle was 1.5～3g/L in the reaction soln, SiO
2Concentration be 1～5g/L.The pH of reaction soln is transferred between 8～10.Stirring velocity is to react 8～30 hours under the condition of 200～1000rpm.When the organosilicon source coats, alcohol in the mixed solvent of alcohol and water can be methyl alcohol, ethanol, propyl alcohol, butanols etc., the volumn concentration of alcohol is 30～100% in the mixed solvent, the volumn concentration of water is 0～70%, the adding mass percent concentration is 25～28% strong aqua in above-mentioned solution, in the mixing solutions of Xing Chenging, the concentration of ferrite nano particles is 0.015～0.5g/L thus, and the volumetric molar concentration of ammoniacal liquor in reaction soln is 0.5～1mol/L.Dropwise add tetraethoxy 0.01～1ml/L then under the stirring velocity of 200～600rpm, that is, the dropwise add-on of tetraethoxy is that finally to make the tetraethoxy concentration in the reaction system be 0.01～1ml/L, reacts 6～30 hours.Can obtain being of a size of ferrite-silica core core/shell nanoparticles of 50～200nm by the control of reaction conditions.Can see that by transmission electron microscope the number of the ferrite nano particles that this core-shell particles contains can be 10～50.
Dropwise adding tetraethoxy during above-mentioned organosilicon source coats, tetraethoxy can add in batches, each add-on is, making the tetraethoxy concentration in the reaction system is 0.01～0.05ml/L, wherein the timed interval of adjacent twice adding is 3～6h, after tetraethoxy all adds, continue reaction 6～30h again.By the add-on of control tetraethoxy, can regulate the thickness of coated with silica layer of ferrite-silica core core/shell nanoparticles of last formation and the size of resulting core-shell particles.
This preparation method is before carrying out coated with silica to ferrite nano particles, earlier ferrite nano particles is done supersound process, this can increase the surface charge of ferrite nano particles, the amount of surface charge many than lacking of peptization ferrite nano particles and than surface treated ferrite nano particles not, thereby the interaction strength between the ferrite nano particles of supersound process is between peptization ferrite nano particles and not surface treated ferrite nano particles.So utilize the ferrite nano particles synthetic ferrite-silica core core/shell nanoparticles of supersound process and compare check figure with peptization ferrite nano particles synthetic core-shell particles and want many, though and with compare check figure with not surface treated ferrite nano particles synthetic core-shell particles few, the size of particle is much smaller.Test result shows, the particle diameter of the ferrite-silica core core/shell nanoparticles that makes with method of the present invention is about 50～200nm, and the ferrite particle number that is coated in each particulate is about 10～50 scopes.That is, the ferrite-silica core core/shell nanoparticles preparation method with supersound process of the present invention can synthesize the ferrite that check figure is more and size is less-silica core core/shell nanoparticles, remedy the deficiencies in the prior art.
As mentioned above, the present invention utilizes the way of supersound process ferrite nano particles, under the reaction conditions of gentleness, synthesized ferrite-silica core core/shell nanoparticles by simple technological process, this particle has following characteristics: the number of (1) magnetic kernel is more, the content height of magnetic substance, the size of particle can be controlled at 50～200nm; (2) compact structure of coated with silica layer, thereby chemical stability height, resistance of oxidation is strong; (3) do not have exposed magnetic particle, and good leak integrity is arranged; (4) Biao Mian chemical constitution is a silicon-dioxide, and easily further functionalization utilizes the silylating reagent that has groups such as amino, sulfydryl, epoxy that silica sphere is modified, and can obtain having the surface of functional groups such as amino, sulfydryl, epoxy.
Ferrite-silica core the core/shell nanoparticles of the present invention's preparation can be widely used in biological field, as the treatment of nuclear magnetic resonance, bioseparation, biomarker, drug delivery and some diseases, also can be used for sealing and magnetic recording material.
Embodiment
Embodiment 1:Fe
3O
4The preparation of nanoparticle
Take by weighing the FeCl of 12.48g
36H
2The FeCl of O and 4.60g
24H
2O, the water dissolution of passing through letting nitrogen in and deoxidizing with 100ml obtains mixing solutions.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 20ml is the strong aqua of 25-28%, rapidly to wherein pouring above-mentioned molysite mixing solutions into, reacts 1h down at 80 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the Fe that particle diameter is 6～10nm 3～5 times with the high purity water cleaning
3O
4Nanoparticle.
Embodiment 2: γ-Fe
2O
3The preparation of nanoparticle
Take by weighing the FeCl of 12.48g
36H
2The FeCl of O and 4.60g
24H
2O, the water dissolution of passing through letting nitrogen in and deoxidizing with 100ml obtains mixing solutions.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 20ml is the strong aqua of 25-28%, rapidly to wherein pouring above-mentioned molysite mixing solutions into, reacts 1h down at 80 ℃ under vigorous stirring.Aerating oxygen 2h in reaction soln then.After reaction finishes, isolate red solid with the permanent magnet of 0.1T from reaction soln, the gained solid cleans with high purity water and promptly gets γ-Fe that particle diameter is 6～10nm 3～5 times
2O
3Nanoparticle.
Embodiment 3:CoFe
2O
4The preparation of nanoparticle
Take by weighing the CoCl of 12.66g
36H
2The FeCl of O and 4.60g
24H
2O, the water dissolution of passing through letting nitrogen in and deoxidizing with 100ml obtains mixing solutions.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 20ml is the strong aqua of 25-28%, rapidly to wherein pouring above-mentioned mixing salt solution into, reacts 1h down at 50 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the CoFe that particle diameter is 3～13nm 3～5 times with the high purity water cleaning
2O
4Nanoparticle.
Embodiment 4: the inorganic silicon source coats (coated with silica for the first time)
Take by weighing 1.4g Na
2SiO
3(SiO
2Content is 45%) be dissolved in the 400ml water, be 9.2 with the pH of resin cation (R.C.) regulator solution.Get the above-mentioned synthetic Fe of 0.8g
3O
4Nanoparticle joins in the 100ml water, at this moment Fe
3O
4The surface potential of nanoparticle is-7.10mV, ultrasonic 15min in the ultrasonic wave of 40kHz then, Fe
3O
4The surface potential of nanoparticle is-20.03mV.With top Na
2SiO
3And Fe
3O
4Solution at room temperature, reacts 12h with the 300rpm stirring velocity after mixing in the 1L round-bottomed flask.After reaction finishes, use magnetic separator column separated product from reaction soln, and promptly get the Fe that particle diameter is the coated with silica of 7～12nm 3～5 times with the high purity water cleaning
3O
4Nanoparticle.
Embodiment 5: the organosilicon source coats (coated with silica for the second time)
The strong aqua, 0.008g that add 400ml ethanol, 100ml water, 30ml mass percent concentration successively and be 25-28% in the 1L round-bottomed flask are through the coated with silica synthetic Fe first time
3O
4Nanoparticle.At room temperature, drip the 0.03ml tetraethoxy, reaction 12h with the 300rpm stirring velocity.With magnetic separator column separated product from reaction soln, and clean 3～5 times with high purity water and promptly get the multinuclear Fe that median size is 50nm
3O
4-SiO
2Nucleocapsid grain particle.
Get above-mentioned core-shell particles 0.210g and be dispersed among the 10ml 1M HCl and soak 10min, the iron concentration of leakage is 3.1ppm.
As above reaction ratio adds the 0.03ml tetraethoxy, behind the reaction 5h, adds the 0.05ml tetraethoxy again, continues reaction 12h.With magnetic separator column separated product from reaction soln, and clean 3～5 times with high purity water and promptly get the multinuclear Fe that particle diameter is 100nm
3O
4-SiO
2Nucleocapsid grain particle.
Embodiment 6: with the nanometer Fe in embodiment 4,5 processes
3O
4Particle changes γ-Fe into
2O
3And/or CoFe
2O
4Nanoparticle, the preparation process of employing embodiment 4,5 can make γ-Fe
2O
3-silica core-shell particulate and/or CoFe
2O
4-silica core-shell particulate.
Claims (5)
1,---the technological process that surface treatment---coating of inorganic silicon source---organosilicon source coats that a kind of supersound process prepares the method for ferrite-silica core core/shell nanoparticles, and the preparation ferrite nano particles is arranged; Said preparation ferrite nano particles is to prepare ferrite nano particles with coprecipitation method; It is ferrite nano particles to be added in contain SiO that said inorganic silicon source coats
2The aqueous solution of water-soluble inorganic salt in stir; Said organosilicon source coats, the ferrite nano particles of finishing the coating of inorganic silicon source is distributed in the mixed solvent of alcohol and water, under the ammonification water condition, undertaken by teos hydrolysis and condensation reaction, it is characterized in that, said surface treatment is that ferrite nano particles is done supersound process, and washed ferrite nano particles is made into the aqueous solution of 0.25～10g/L, is supersound process 5～60 minutes in 20～80kHz ultrasonic wave in frequency.
2, prepare the method for ferrite-silica core core/shell nanoparticles according to the described supersound process of claim 1, it is characterized in that, said inorganic silicon source coats, and the concentration of ferrite nano particles is 1.5～3g/L in the reaction soln, SiO
2Concentration be 1～5g/L, the pH of reaction soln is transferred between 8～10, stirring velocity is to react 8～30 hours under the condition of 200～1000rpm; Said organosilicon source coats, the concentration of ferrite nano particles is 0.015～0.5g/L, the volumetric molar concentration of ammoniacal liquor is 0.5～1mol/L, under the stirring velocity of 200～600rpm, dropwise add tetraethoxy, finally making the tetraethoxy concentration in the reaction system is 0.01～1ml/L, reacts 6～30 hours.
3, the method for preparing ferrite-silica core core/shell nanoparticles according to claim 1 or 2 described supersound process, it is characterized in that, said organosilicon source coats, tetraethoxy adds in batches, each add-on is that to make the tetraethoxy concentration in the reaction system be 0.01～0.05ml/L, the timed interval of adjacent twice adding is 3～6 hours, after tetraethoxy all adds, continues reaction 6～30 hours again.
4, prepare the method for ferrite-silica core core/shell nanoparticles according to claim 1 or 2 described supersound process, it is characterized in that said ferrite nano particles is γ-Fe
2O
3And/or CoFe
2O
4Nanoparticle.
5, prepare the method for ferrite-silica core core/shell nanoparticles according to the described supersound process of claim 3, it is characterized in that, said ferrite nano particles is γ-Fe
2O
3And/or CoFe
2O
4Nanoparticle.
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