CN110451580A - A method of preparing monodisperse ferroferric oxide magnetic nano-particles - Google Patents
A method of preparing monodisperse ferroferric oxide magnetic nano-particles Download PDFInfo
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- CN110451580A CN110451580A CN201910793602.XA CN201910793602A CN110451580A CN 110451580 A CN110451580 A CN 110451580A CN 201910793602 A CN201910793602 A CN 201910793602A CN 110451580 A CN110451580 A CN 110451580A
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- ferroferric oxide
- magnetic nano
- magneto separate
- oxide magnetic
- preparing monodisperse
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 20
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 17
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 12
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 11
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 11
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000006228 supernatant Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 38
- 239000002245 particle Substances 0.000 abstract description 31
- 239000002105 nanoparticle Substances 0.000 abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 10
- 230000004048 modification Effects 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 10
- 229940056319 ferrosoferric oxide Drugs 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 239000011324 bead Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 238000000926 separation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000003958 hematopoietic stem cell Anatomy 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 210000001178 neural stem cell Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0018—Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Compounds Of Iron (AREA)
- Soft Magnetic Materials (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention belongs to inorganic nano material preparation process technology fields, more particularly to a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles.First by ferric acetyl acetonade, disodium ethylene diamine tetraacetate, sodium acetate trihydrate after completely dissolution, carries out solvent thermal reaction in mixed alkoxide solution, after supersound washing and Magneto separate, using after vacuum drying up to purpose product.The highly uniform bead of the size of monodisperse magnetic ferriferrous oxide nano-particle prepared by the present invention, Unusually narrow particle size distribution, particle diameter distribution are in normal distribution, and 90% particle diameter distribution is at 25 ± 5 nanometers.Ferroso-ferric oxide particle surface charge density height, surface modification carboxyl, aqueous dispersion are good, can be widely used in Magneto separate enriching and recovering technical field of research.
Description
Technical field
The present invention relates to a kind of methods for preparing magnetic ferroferric oxide nanometer material, belong to inorganic nano material preparation work
Skill technical field.
Background technique
Ferroso-ferric oxide (Ferroferric Oxide), chemical formula Fe3O4.It is referred to as iron oxide black in industry, inhales iron
Stone, Black Rouge, because it is the magnetic black powder of tool, so the magnetic iron oxide that is otherwise known as.Ferroso-ferric oxide is a kind of
Less toxic material, rat mouthful is through LD50: > 5gm/kg, and mouse introduces peritonaeum LD50:1890mg/kg.Due to the low toxicity of ferroso-ferric oxide
Characteristic is often widely used in biological medicine separation and concentration field.
Separation and concentration includes two chemically and physically technical process connected each other of separation and enrichment.It is led in medicinal application
Drug is loaded onto presumptive area using externally-applied magnetic field by domain, carrier of the immune magnetic material as medicine-releasing system, can make immune magnetic
Property material on anticancer drug be easier to contact with cancer cell, improve killing cancer cell effect.In terms of biologic applications, magnetic is immunized
Property material the various cells of the mankind can be separated by direct method and indirect method, such as red blood cell, neural stem cell, hematopoietic cell, T leaching
Bar cell etc..The brief technical process of Magneto separate is: will be added in conjunction with the magnetic material of sample to be separated containing needing point
From in the solution of sample, after waiting magnetic materials sufficiently to be combined with sample to be separated, outer magnetic is applied to solution by magnetic separating apparatus
, the magnetic material that sample to be separated is combined under the action of external magnetic field is enriched with from solution to be come out, to realize to be separated
The separation of sample.
The magnetic separation technique of ferroso-ferric oxide applies that convenient and efficient, required equipment is simple, extraction efficiency high point.Single point
Granular media system typically refers to the dispersion of dispersed phase single variety and Unusually narrow particle size distribution (i.e. the partial size overwhelming majority is equal), partial size
Distribution is in normal distribution.Since monodisperse ferroferric oxide magnetic nano-particles have, enrichment target is single, bioaccumulation efficiency is high
Feature.How efficiently largely to prepare monodisperse magnetic nano ferriferrous oxide particle is that the field is urgently to be resolved at present
Research topic.
Summary of the invention
The present invention is directed to provide a kind of simple process in place of overcome the deficiencies in the prior art, four oxygen of monodisperse magnetic is prepared
Change the method for three Fe nanometer particles.Magnetic ferroferric oxide nanoparticle size prepared by the present invention is distributed very narrow, particle diameter distribution
In normal distribution, 90% particle diameter distribution is at 25 ± 5 nanometers, and magnetism is between superparamagnetic and ferromagnetism.Ferroso-ferric oxide grain
Sub- surface modification carboxyl, particle surface charge density height, surface modification carboxyl, aqueous dispersion are good, can be in Magneto separate richness
Collection recovery technology research field is widely used.
In order to achieve the above objectives, the present invention is implemented as follows:
A method of monodisperse ferroferric oxide magnetic nano-particles being prepared, by ferric acetyl acetonade, disodium ethylene diamine tetraacetate
And sodium acetate trihydrate in mixed alkoxide solution after completely dissolution, first carry out three-D high frequency resonance processing, then to carry out solvent heat anti-
It answers, after supersound washing and Magneto separate, using being dried in vacuo up to purpose product.
As a preferred embodiment, ferric acetyl acetonade of the present invention, disodium ethylene diamine tetraacetate and sodium acetate trihydrate
Mass ratio be followed successively by 1:0.1~1:0.2~5；
Further, the concentration of ferric acetyl acetonade of the present invention is 0.02~0.3 g/mL.
Further, mixed alkoxide solution of the present invention is the mixture of ethylene glycol and polyethylene glycol -200；The second
The volume ratio of glycol and polyethylene glycol -200 is 1:0.1~10.
Further, mixed alkoxide solution of the present invention be ethylene glycol and polyethylene glycol -200 after mixing, at 100 DEG C
Stir 2 hours mixed solutions formed.
Further, the circle frequency vibration dynamic frequency of three-D high frequency resonance processing of the present invention is 100~120 hertz, when
Between be 8~15 seconds, obtain mixture.
Further, for solvent thermal reaction temperature of the present invention at 150~220 DEG C, the reaction time is 6~48 hours.
Further, supersound washing of the present invention and Magneto separate step include:
(1) supernatant is outwelled, the mixture of bottom black product ethyl alcohol and deionized water is transferred in beaker；The ethyl alcohol
Volume ratio with deionized water is 1:1；
(2) beaker is put into after being cleaned by ultrasonic in ultrasonic cleaning machine, places magnet thereunder, removes supernatant under magnetic fields
Liquid repeats above-mentioned Magneto separate and operates 3 times；
(3) above-mentioned Magneto separate is repeated with deionized water to operate 3 times, finally disperse black product in deionized water.
Further, vacuum drying condition of the present invention: temperature is controlled at 50~70 DEG C；Vacuum degree control is -0.05
~-0.1 Mpa；Time is 1~3 hour.
Compared with prior art, the present invention has a characteristic that
(1) distribution of magnetic ferroferric oxide nanoparticle size is very narrow, and particle diameter distribution is in normal distribution, and 90% particle diameter distribution exists
25 ± 5 nanometers, magnetism is between superparamagnetic and ferromagnetism.Ferroso-ferric oxide particle surface modifies carboxyl, can apply
In Magneto separate enriching and recovering device.
(2) the Magneto separate enriching and recovering speed of magnetic ferroferric oxide nanoparticle is fast, at 10.0 KOe of magnetic field strength,
Ferriferrous oxide nano-particle in concentration and separation 1g/10mL aqueous solution needs 3.5~4.0 seconds, and the rate of recovery is 99.5~
99.9%。
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and specific embodiments.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is the XRD diffraction pattern figure of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Fig. 2 is the FT-IR spectrogram of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Fig. 3 is the SEM figure of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Fig. 4 is the SEM figure of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Fig. 5 is the SEM figure of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Fig. 6 is the SEM figure of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Fig. 7 is the SEM figure of monodisperse ferroferric oxide magnetic nano-material prepared by the present invention.
Specific embodiment
The present invention is by ferric acetyl acetonade, disodium ethylene diamine tetraacetate, and sodium acetate trihydrate is sufficiently molten in mixed alkoxide solution
Xie Hou first carries out three-D high frequency resonance processing, then carries out solvent thermal reaction, after supersound washing and Magneto separate, using true
Up to purpose product after sky is dry, preparation step is:
(1) above-mentioned ferric acetyl acetonade, disodium ethylene diamine tetraacetate, the mass ratio of sodium acetate trihydrate be 1:0.1~1:0.2~
5；Above-mentioned acetylacetone,2,4-pentanedione concentration of iron is 0.02~0.2 g/mL.
(2) the above-mentioned mixed alkoxide solution is the mixture of ethylene glycol and polyethylene glycol -200；Above-mentioned hydramine is mixed
It closes after solution stirs 2 hours at 100 DEG C for the mixture of ethylene glycol and polyethylene glycol -200 and reuses；Above-mentioned ethylene glycol:
The volume ratio of polyethylene glycol -200 is 1:0.1~10.
(3) the circle frequency vibration dynamic frequency of above-mentioned three-D high frequency resonance processing is 100~120 hertz, and the time is 8~15 seconds,
Obtain mixture.
(4) for above-mentioned solvent thermal reaction temperature at 150~220 DEG C, the reaction time is 6~48 hours.
(5) above-mentioned Magneto separate and washing operation process flow are first to outwell supernatant, bottom black product ethyl alcohol
It is transferred in beaker with the mixture (volume ratio is=1:1) of deionized water.Beaker is put into ultrasonic cleaning machine after ultrasound, In
Magnet is placed below, these magnetic nano-particle rapid aggregations remove supernatant in beaker bottom under magnetic field, repeat above-mentioned
Magneto separate operates 3 times.Above-mentioned Magneto separate is repeated with deionized water again to operate 3 times, and black product is finally dispersed in deionized water
In.
(6) condition of above-mentioned vacuum drying operation technological process, temperature be 50~70 DEG C, vacuum degree be -0.05~-
0.1 Mpa, time are 1~3 hour.
It is the XRD diffraction pattern figure of magnetic ferroferric oxide nanometer material prepared by the present invention referring to Fig. 1, it can be seen that
Product is ferroso-ferric oxide, and three strongest peak is respectively (311), (440), (511) its PDF card number are as follows: 03-0863.Fig. 2 is the present invention
Magnetic ferroferric oxide nanometer material FT-IR spectrogram, it can be seen that ferroso-ferric oxide surface modification carboxyl.Fig. 3~7 are
The SEM of monodisperse magnetic ferroferric oxide magnetic nano-particles prepared by the present invention schemes, it can be seen that ferriferrous oxide nano grain
The highly uniform bead of the shape size of son, Unusually narrow particle size distribution (i.e. the partial size overwhelming majority is equal), particle diameter distribution is in just
State distribution, 90% particle diameter distribution is at 25 ± 5 nanometers.
Embodiment 1
After being stirred 2 hours at 100 DEG C after ethylene glycol and polyethylene glycol -200 are sufficiently mixed according to volume ratio for 1:0.1 again
It uses.By ferric acetyl acetonade, disodium ethylene diamine tetraacetate, sodium acetate trihydrate is 1:0.1:3 in above-mentioned alcohol according to mass ratio
It is sufficiently dissolved in mixed solution, wherein the concentration of ferric acetyl acetonade is 0.3 g/mL.Three-D high frequency is first carried out to above-mentioned mixed liquor
The circle frequency vibration dynamic frequency of resonance processing, three-D high frequency resonance processing is 100 hertz, and the time is 15 seconds, obtains mixture.It is above-mentioned mixed
It closes object and carries out solvent thermal reaction, temperature is 200 DEG C, and the reaction time is 10 hours.After supersound washing and Magneto separate, then pass through
It crosses and is dried in vacuo up to purpose product.Magneto separate and washing operation process flow are first to outwell supernatant, bottom black product
It is transferred in beaker with the mixture (volume ratio is=1:1) of ethyl alcohol and deionized water.Beaker is put into ultrasonic cleaning machine ultrasonic
Afterwards, magnet is placed thereunder, these magnetic nano-particle rapid aggregations remove supernatant in beaker bottom under magnetic field, weight
Multiple above-mentioned Magneto separate operates 3 times.Above-mentioned Magneto separate is repeated with deionized water again to operate 3 times, is finally dispersed in black product
In ionized water.It is dried in vacuo the condition of operation technological process, temperature is 70 DEG C, and vacuum degree is -0.1 Mpa, and the time is 1 hour.
The highly uniform bead of the size of prepared monodisperse magnetic ferriferrous oxide nano-particle, size distribution is very
Narrow (i.e. the partial size overwhelming majority is equal), particle diameter distribution are in normal distribution, and 90% particle diameter distribution is at 25 ± 5 nanometers.Four oxidations three
The Magneto separate enriching and recovering speed of iron particle surface modification carboxyl, magnetic ferroferric oxide nanoparticle is fast, in magnetic field strength
Under 10.0 KOe, the ferriferrous oxide nano-particle in concentration and separation 1g/10mL aqueous solution needs 3.5 seconds, and the rate of recovery is
99.5%。
Embodiment 2
After being stirred 2 hours at 100 DEG C after ethylene glycol and polyethylene glycol -200 are sufficiently mixed according to volume ratio for 1:0.5 again
It uses.By ferric acetyl acetonade, disodium ethylene diamine tetraacetate, sodium acetate trihydrate is 1:0.1:3 in above-mentioned alcohol according to mass ratio
It is sufficiently dissolved in mixed solution, wherein the concentration of ferric acetyl acetonade is 0.3 g/mL.Three-D high frequency is first carried out to above-mentioned mixed liquor
The circle frequency vibration dynamic frequency of resonance processing, three-D high frequency resonance processing is 120 hertz, and the time is 8 seconds, obtains mixture.It is above-mentioned mixed
It closes object and carries out solvent thermal reaction, temperature is 200 DEG C, and the reaction time is 10 hours.After supersound washing and Magneto separate, then pass through
It crosses and is dried in vacuo up to purpose product.Magneto separate and washing operation process flow are first to outwell supernatant, bottom black product
It is transferred in beaker with the mixture (volume ratio is=1:1) of ethyl alcohol and deionized water.Beaker is put into ultrasonic cleaning machine ultrasonic
Afterwards, magnet is placed thereunder, these magnetic nano-particle rapid aggregations remove supernatant in beaker bottom under magnetic field, weight
Multiple above-mentioned Magneto separate operates 3 times.Above-mentioned Magneto separate is repeated with deionized water again to operate 3 times, is finally dispersed in black product
In ionized water.It is dried in vacuo the condition of operation technological process, temperature is 70 DEG C, and vacuum degree is -0.1 Mpa, and the time is 1 hour.
The highly uniform bead of the size of prepared monodisperse magnetic ferriferrous oxide nano-particle, size distribution is very
Narrow (i.e. the partial size overwhelming majority is equal), particle diameter distribution are in normal distribution, and 90% particle diameter distribution is at 25 ± 5 nanometers.Four oxidations three
The Magneto separate enriching and recovering speed of iron particle surface modification carboxyl, magnetic ferroferric oxide nanoparticle is fast, in magnetic field strength
Under 10.0 KOe, the ferriferrous oxide nano-particle in concentration and separation 1g/10mL aqueous solution needs 4.0 seconds, and the rate of recovery is
99.9%。
Embodiment 3
Make again after being stirred 2 hours at 100 DEG C after ethylene glycol and polyethylene glycol -200 are sufficiently mixed according to volume ratio for 1:1
With.By ferric acetyl acetonade, disodium ethylene diamine tetraacetate, sodium acetate trihydrate is 1:0.2:4 mixed in above-mentioned alcohol according to mass ratio
It closes and is sufficiently dissolved in solution, wherein the concentration of ferric acetyl acetonade is 0.1 g/mL.It is total that three-D high frequency is first carried out to above-mentioned mixed liquor
The circle frequency vibration dynamic frequency of vibration processing, three-D high frequency resonance processing is 110 hertz, and the time is 12 seconds, obtains mixture.Above-mentioned mixing
Object carries out solvent thermal reaction, and temperature is 200 DEG C, and the reaction time is 12 hours.After supersound washing and Magneto separate, using
It is dried in vacuo up to purpose product.Magneto separate and washing operation process flow are first to outwell supernatant, and bottom black product is used
Ethyl alcohol and the mixture (volume ratio is=1:1) of deionized water are transferred in beaker.Beaker is put into ultrasonic cleaning machine ultrasonic
Afterwards, magnet is placed thereunder, these magnetic nano-particle rapid aggregations remove supernatant in beaker bottom under magnetic field, weight
Multiple above-mentioned Magneto separate operates 3 times.Above-mentioned Magneto separate is repeated with deionized water again to operate 3 times, is finally dispersed in black product
In ionized water.It is dried in vacuo the condition of operation technological process, temperature is 60 DEG C, and vacuum degree is -0.1 Mpa, and the time is 2 hours.
The highly uniform bead of the size of prepared monodisperse magnetic ferriferrous oxide nano-particle, size distribution is very
Narrow (i.e. the partial size overwhelming majority is equal), particle diameter distribution are in normal distribution, and 90% particle diameter distribution is at 25 ± 5 nanometers.Four oxidations three
The Magneto separate enriching and recovering speed of iron particle surface modification carboxyl, magnetic ferroferric oxide nanoparticle is fast, in magnetic field strength
Under 10.0 KOe, the ferriferrous oxide nano-particle in concentration and separation 1g/10mL aqueous solution needs 3.8 seconds, and the rate of recovery is
99.8%。
Embodiment 4
After being stirred 2 hours at 100 DEG C after ethylene glycol and polyethylene glycol -200 are sufficiently mixed according to volume ratio for 1:0.1 again
It uses.By ferric acetyl acetonade, disodium ethylene diamine tetraacetate, sodium acetate trihydrate is 1:0.2:5 in above-mentioned alcohol according to mass ratio
It is sufficiently dissolved in mixed solution, wherein the concentration of ferric acetyl acetonade is 0.1 g/mL.Three-D high frequency is first carried out to above-mentioned mixed liquor
The circle frequency vibration dynamic frequency of resonance processing, three-D high frequency resonance processing is 110 hertz, and the time is 10 seconds, obtains mixture.It is above-mentioned mixed
It closes object and carries out solvent thermal reaction, temperature is 200 DEG C, and the reaction time is 10 hours.After supersound washing and Magneto separate, then pass through
It crosses and is dried in vacuo up to purpose product.Magneto separate and washing operation process flow are first to outwell supernatant, bottom black product
It is transferred in beaker with the mixture (volume ratio is=1:1) of ethyl alcohol and deionized water.Beaker is put into ultrasonic cleaning machine ultrasonic
Afterwards, magnet is placed thereunder, these magnetic nano-particle rapid aggregations remove supernatant in beaker bottom under magnetic field, weight
Multiple above-mentioned Magneto separate operates 3 times.Above-mentioned Magneto separate is repeated with deionized water again to operate 3 times, is finally dispersed in black product
In ionized water.It is dried in vacuo the condition of operation technological process, temperature is 70 DEG C, and vacuum degree is -0.1 Mpa, and the time is 1 hour.
The highly uniform bead of the size of prepared monodisperse magnetic ferriferrous oxide nano-particle, size distribution is very
Narrow (i.e. the partial size overwhelming majority is equal), particle diameter distribution are in normal distribution, and 90% particle diameter distribution is at 25 ± 5 nanometers.Four oxidations three
The Magneto separate enriching and recovering speed of iron particle surface modification carboxyl, magnetic ferroferric oxide nanoparticle is fast, in magnetic field strength
Under 10.0 KOe, the ferriferrous oxide nano-particle in concentration and separation 1g/10mL aqueous solution needs 3.6 seconds, and the rate of recovery is
99.6%。
Embodiment 5
After being stirred 2 hours at 100 DEG C after ethylene glycol and polyethylene glycol -200 are sufficiently mixed according to volume ratio for 1:0.2 again
It uses.By ferric acetyl acetonade, disodium ethylene diamine tetraacetate, sodium acetate trihydrate is 1:0.1:3 in above-mentioned alcohol according to mass ratio
It is sufficiently dissolved in mixed solution, wherein the concentration of ferric acetyl acetonade is 0.2g/mL.Three-D high frequency is first carried out to above-mentioned mixed liquor
The circle frequency vibration dynamic frequency of resonance processing, three-D high frequency resonance processing is 110 hertz, and the time is 11 seconds, obtains mixture.It is above-mentioned mixed
It closes object and carries out solvent thermal reaction, temperature is 200 DEG C, and the reaction time is 10 hours.After supersound washing and Magneto separate, then pass through
It crosses and is dried in vacuo up to purpose product.Magneto separate and washing operation process flow are first to outwell supernatant, bottom black product
It is transferred in beaker with the mixture (volume ratio is=1:1) of ethyl alcohol and deionized water.Beaker is put into ultrasonic cleaning machine ultrasonic
Afterwards, magnet is placed thereunder, these magnetic nano-particle rapid aggregations remove supernatant in beaker bottom under magnetic field, weight
Multiple above-mentioned Magneto separate operates 3 times.Above-mentioned Magneto separate is repeated with deionized water again to operate 3 times, is finally dispersed in black product
In ionized water.It is dried in vacuo the condition of operation technological process, temperature is 60 DEG C, and vacuum degree is -0.1 Mpa, and the time is 1 hour.
The highly uniform bead of the size of prepared monodisperse magnetic ferriferrous oxide nano-particle, size distribution is very
Narrow (i.e. the partial size overwhelming majority is equal), particle diameter distribution are in normal distribution, and 90% particle diameter distribution is at 25 ± 5 nanometers.Four oxidations three
The Magneto separate enriching and recovering speed of iron particle surface modification carboxyl, magnetic ferroferric oxide nanoparticle is fast, in magnetic field strength
Under 10.0 KOe, the ferriferrous oxide nano-particle in concentration and separation 1g/10mL aqueous solution needs 4.0 seconds, and the rate of recovery is
99.9%。
For those skilled in the art, the invention may be variously modified and varied.It is all in spirit of the invention
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles, it is characterised in that: by ferric acetyl acetonade, second two
Amine tetraacethyl disodium and sodium acetate trihydrate after completely dissolution, first carry out three-D high frequency resonance processing in mixed alkoxide solution, then
Solvent thermal reaction is carried out, after supersound washing and Magneto separate, using being dried in vacuo up to purpose product.
2. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 1, it is characterised in that:
The mass ratio of the ferric acetyl acetonade, disodium ethylene diamine tetraacetate and sodium acetate trihydrate is followed successively by 1:0.1~1:0.2~5.
3. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 2, it is characterised in that:
The concentration of the ferric acetyl acetonade is 0.02~0.3 g/mL.
4. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 3, it is characterised in that:
The mixed alkoxide solution is the mixture of ethylene glycol and polyethylene glycol -200；The volume of the ethylene glycol and polyethylene glycol -200
Than for 1:0.1~10.
5. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 4, it is characterised in that:
The mixed alkoxide solution be ethylene glycol and polyethylene glycol -200 after mixing, the mixing that formation in 2 hours stir at 100 DEG C is molten
Liquid.
6. a kind of according to claim 5 prepare magnetic ferroferric oxide nanometer MATERIALS METHODS, it is characterised in that: described three
The circle frequency vibration dynamic frequency for tieing up high-frequency resonance processing is 100~120 hertz, and the time is 8~15 seconds, obtains mixture.
7. any a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 1~6,
Be characterized in that: for the solvent thermal reaction temperature at 150~220 DEG C, the reaction time is 6~48 hours.
8. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 7, which is characterized in that
The supersound washing and Magneto separate step include:
(1) supernatant is outwelled, the mixture of bottom black product ethyl alcohol and deionized water is transferred in beaker；The ethyl alcohol
Volume ratio with deionized water is 1:1；
(2) beaker is put into after being cleaned by ultrasonic in ultrasonic cleaning machine, places magnet thereunder, removes supernatant under magnetic fields
Liquid repeats above-mentioned Magneto separate and operates 3 times；
(3) above-mentioned Magneto separate is repeated with deionized water to operate 3 times, finally disperse black product in deionized water.
9. a kind of method for preparing monodisperse ferroferric oxide magnetic nano-particles according to claim 8, feature exist
In: the vacuum drying condition: temperature is controlled at 50~70 DEG C；Vacuum degree control is in -0.05~-0.1 Mpa；Time is 1~3
Hour.
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| CN111268742A (en) * | 2020-02-12 | 2020-06-12 | 西安工程大学 | Preparation method of ferroferric oxide quantum dots |
| CN114014371A (en) * | 2021-12-20 | 2022-02-08 | 苏州海狸生物医学工程有限公司 | Method for regulating and controlling particle size uniformity of superparamagnetic ferroferric oxide nano microspheres under assistance of ultrasound |
| CN115010188A (en) * | 2022-01-13 | 2022-09-06 | 渤海大学 | Preparation of nano Co capable of realizing magnetic transformation under temperature control condition 3 O 4 Magnetic material method |
| CN115010187A (en) * | 2022-01-13 | 2022-09-06 | 渤海大学 | Preparation of monodisperse Co 3 O 4 Method for producing magnetic nanoparticles |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111268742A (en) * | 2020-02-12 | 2020-06-12 | 西安工程大学 | Preparation method of ferroferric oxide quantum dots |
| CN114014371A (en) * | 2021-12-20 | 2022-02-08 | 苏州海狸生物医学工程有限公司 | Method for regulating and controlling particle size uniformity of superparamagnetic ferroferric oxide nano microspheres under assistance of ultrasound |
| CN115010188A (en) * | 2022-01-13 | 2022-09-06 | 渤海大学 | Preparation of nano Co capable of realizing magnetic transformation under temperature control condition 3 O 4 Magnetic material method |
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Application publication date: 20191115 |