CN103342393B - Monodisperse superparamagnetic nano crystal colloidal core-shell composite particles and preparation method thereof - Google Patents
Monodisperse superparamagnetic nano crystal colloidal core-shell composite particles and preparation method thereof Download PDFInfo
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- 239000011246 composite particle Substances 0.000 title claims abstract description 12
- 239000011258 core-shell material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002159 nanocrystal Substances 0.000 title abstract 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 29
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 29
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 18
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 11
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001263 FEMA 3042 Substances 0.000 claims description 10
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 10
- 229920002258 tannic acid Polymers 0.000 claims description 10
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 10
- 235000015523 tannic acid Nutrition 0.000 claims description 10
- 229940033123 tannic acid Drugs 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001447 ferric ion Inorganic materials 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 235000004515 gallic acid Nutrition 0.000 claims description 6
- 229940074391 gallic acid Drugs 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 229960001031 glucose Drugs 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 230000005298 paramagnetic effect Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 claims description 2
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229950006191 gluconic acid Drugs 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 abstract description 20
- 239000004038 photonic crystal Substances 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000003086 colorant Substances 0.000 abstract description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920005903 polyol mixture Polymers 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 51
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011805 ball Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
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- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
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- 150000002303 glucose derivatives Chemical class 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Soft Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses monodisperse superparamagnetic nano crystal colloidal core-shell composite particles, which are monodisperse superparamagnetic nano cluster particles which are gathered by ferroferric oxide nanocrystalline. The surfaces of the particles are coated by polyvinylpyrrolidone. The preparation method of the composite particles comprises the following steps: adding trivalent iron salt to polyol mixture solution of polyvinylpyrrolidone and polyhydroxy compounds; agitating until the trivalent iron salt is completely dissolved; adjusting the pH value to 8.0-10.0, then carrying out enclosed heating to 180-240 DEG C, and carrying out heat preservation for 6-48 hours. The monodisperse superparamagnetic nano crystal colloidal core-shell composite particles disclosed by the invention can be assembled into different colors of photonic crystal in a magnetic control manner; the dependency level of the magnetic photonic crystal on the solvent polarity, the ion strength and the pH value can be reduced.
Description
Technical field
The present invention relates to magnetic Nano material preparation field, particularly relate to a kind of monodispersed super-paramagnetic ferriferrous oxide/polyvinylpyrrolidone nanometer crystal druse colloid Core-shell Composite Particles and preparation method thereof.
Background technology
Magnetic responsiveness photonic crystal refers to a kind of Responsive photonic crystals material that the color of material can be controlled by the change of applied field strengths.Purposes quite is widely had at sensing, Display Technique, speculum, the civil area such as energy-conservation.At present achieve major progress with the research of the tri-iron tetroxide sub-micron ball magnetic responsiveness photonic crystal that is primitive.The U.S.'s " advanced material " magazine (Adv.Mater.2001,13rd volume, 1681 pages) report a kind of PS colloid micro ball containing 17% ferritic superparamagnetic, but in colloid primitive, the content of magnetic component is too low, so interparticle distance adjustable extent is less can not realize full spectrum variable color.Germany " applied chemistry " magazine (Angew.Chem.Int.Edit.2007,46th volume, 7428 pages) report the coated superparamagnetic secondary aggregate be made up of ferriferrous oxide nano crystalline substance of polyacrylic acid, when being scattered in the aqueous solution, under the effect of externally-applied magnetic field, one-dimensional nano structure diffracts visible light can be arranged in, and full spectrum variable color (450nm-730nm) can be realized.But can only develop the color in aqueous, limit the range of application of magnetic photonic crystal, how producing stronger repulsive force in the non-aqueous solvent that polarity is more weak becomes the obstacle widening magnetic photonic crystal range of application.The U.S.'s " advanced material " magazine (Adv.Mater.2009,21st volume, 4259 pages) report a kind of tri-iron tetroxide sub-micron ball of coated with silica, the compatibility of dependence silicon dioxide and alkanol can at alkanols (methyl alcohol, ethanol, ethylene glycol, glycerine etc.) disperse in solvent, and can rely on silicon dioxide with surface charge can variable color in alkanol solvent under the effect of externally-applied magnetic field from this sub-micron ball.But the above all methods reported are all rely on electrostatic repulsion as long-range repulsive force to construct photonic crystal, and electrostatic repulsion be one very easily by solvent polarity, the active force of ionic strength and pH value impact.This also just limits existing magnetic photonic crystal and can only combine with hydrophilic non-ionic resin and prepare optics, and in building-up process with deposit the impact (change of such as ionic strength and pH value) that is very easily subject to external environment condition in process and make its performance weaken, the range of application that greatly limit existing photon crystal material improves its long-time stability.The present invention is directed to above problem, prepared and replaced electrostatic repulsion to balance the magnetic nano-particle of externally-applied magnetic field with polyvinyl pyrrolidone polymers layer to produce sterically hindered repulsive force.Make this particle better can disperse in the solvent of opposed polarity and have wider color change interval under additional magnetic fields, and its color change interval is not subject to the impact of effects of ion intensity and pH value.
Summary of the invention
Technical problem to be solved by this invention is: rely on electrostatic repulsion as long-range repulsive force for existing magnetic photonic crystal, thus the operating distance of repulsive force significantly declines with the polarity reduction of solvent and is very easily subject to the shortcoming of the impact of ionic strength and pH value, provides a kind of preparation method of superparamagnetic colloidal particle of space stability ultimate load to solve the problems referred to above.
The present invention solves its technical problem and adopts following technical scheme:
Monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles provided by the invention, be a kind of monodisperse, ultra paramagnetic nanometer crystal druse particle assembled by ferriferrous oxide nano crystalline substance, this particle surface is coated by polyvinylpyrrolidone.
Monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles provided by the invention, its preparation method adopts the method comprised the following steps:
(1) polyol and polyvinylpyrrolidone are added in polyalcohol and be mixed with uniform mixed solution, described polyol, the concentration of polyvinylpyrrolidone are respectively (0.33 ~ 13.3) g/L, (16.7 ~ 400) g/L;
(2) add in mixed solution by trivalent iron salt, be stirred to and dissolve completely, in solution, ferric ion concentration is (1.12 ~ 8.6) g/L, and adjust ph is to 8.0-10.0;
(3) solution of step (2) is put into polytetrafluoroethylene stainless steel cauldron, be airtightly heated to 180-240 DEG C, and be incubated 6-48 hour, obtain monodispersed super-paramagnetic ferriferrous oxide/polyvinylpyrrolidone nanometer crystal druse colloid Core-shell Composite Particles.
Described polyol can be one in glucose, tannic acid, gallic acid or mixture.
Described polyol can be the derivative of glucose, tannic acid, gallic acid.
Described polyalcohol can be ethylene glycol or tirethylene glycol.
Described trivalent iron salt can be the one in iron chloride hexahydrate, ferric trichloride, ferric sulfate, ferric sulfate hydrate, or mixture.
The present invention can use one in sodium acetate, potassium acetate, NaOH, potassium hydroxide or mixture, the pH value described in regulating step (2).
The present invention compared with prior art has following major advantage:
One, replaces electrostatic repulsion to construct magnetic responsiveness photonic crystal with steric-hindrance repulsive force.The present invention is mainly by adopting polyol (as: glucose, tannic acid or gallic acid or their mixture; ) conduct once nanocrystalline inhibitor, polyvinylpyrrolidone is as the dispersant of nanometer crystal druse.
Its two, the product prepared by the present invention have height chemistry and colloidal stability.Rely on the polyvinylpyrrolidone space bit resistance layer on surface, improve the dispersion stabilization of magnetic particle in various solvent (water, dimethyl sulfoxide (DMSO), dimethyl formamide, acetic acid, alkanol, carrene etc.).
Its three, magnetic control of the present invention assembles the photonic crystal of different colours, and the metachrosis that prepared product can make magnetic photonic crystal is by the impact of solvent polarity.Because Surface coating has the polymeric layer of polyvinylpyrrolidone, and sterically hindered active force comes from the Swelling Capacity of its surface polyvinylpyrrolidone and different organic solvents, relevant with the solvability of solvent to polyvinylpyrrolidone.Also making this variable color liquid in different solvents, by applying externally-applied magnetic field, thus showing wider color change interval.
Its four, the product prepared by the present invention can improve the resistivity of magnetic photonic crystal for ionic strength and pH value.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope image of product in embodiments of the invention 1.
Fig. 2 is the X ray diffracting spectrum of product in embodiments of the invention 1.
Fig. 3 is the infrared spectrogram of product in embodiments of the invention 1.
Fig. 4 is the thermogravimetric analysis figure of product in embodiments of the invention 1.
Fig. 5 is the mangneto loop line figure of product in embodiments of the invention 1.
Fig. 6 is the cold curve chart of field cold-peace null field of product in embodiments of the invention 1.
Fig. 7 is the scanning electron microscope diagram of product in embodiment 2.
Fig. 8 is the scanning electron microscope diagram of product in embodiment 2.
Fig. 9 is the scanning electron microscope diagram of product in embodiment 3.
Figure 10 is the scanning electron microscope diagram of product in embodiment 3.
Figure 11 is the scanning electron microscope diagram of product in embodiment 4.
Figure 12 is the scanning electron microscope diagram of product in embodiment 4.
Figure 13 is the scanning electron microscope diagram of product in embodiment 5.
Figure 14 is the variable color light spectrogram of product in dimethyl formamide (DMF) solvent in embodiment 1.
Figure 15 is product variable color light spectrogram in ethanol in embodiment 1.
Figure 16 is the variable color light spectrogram of product in carrene (DCM) in embodiment 1.
Figure 17 is the variable color light spectrogram of product in dimethyl sulfoxide (DMSO) (DMSO) in embodiment 1.
Figure 18 is the variable color light spectrogram of product in acetic acid solvent in embodiment 1.
Figure 19 be in embodiment 1 product at the variable color light spectrogram of diethylene glycol.
Figure 20 is the variable color light spectrogram of product in n-hexyl alcohol in embodiment 1.
Figure 21 is the variable color light spectrogram of product when sodium chloride concentration is 0M in 20% water-80% ethanolic solution in embodiment 1.
Figure 22 is the variable color light spectrogram of product when sodium chloride concentration is 0.05M in 20% water-80% ethanolic solution in embodiment 1.
Figure 23 is the variable color light spectrogram of product when sodium chloride concentration is 0.1M in 20% water-80% ethanolic solution in embodiment 1.
Figure 24 is the variable color light spectrogram of product when pH is 3.0 in 20% water-80% ethanolic solution in embodiment 1.
Figure 25 is the variable color light spectrogram of product when pH is 7.0 in 20% water-80% ethanolic solution in embodiment 1.
Figure 26 is the variable color light spectrogram of product when pH is 10.0 in 20% water-80% ethanolic solution in embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but do not limit the present invention.
Embodiment 1
Glucose and polyvinylpyrrolidone are added in ethylene glycol and be mixed with uniform mixed solution, concentration of glucose is 10g/L, and polyvinylpyrrolidone concentration is 100g/L.Add in mixed solution by ferric chloride hexahydrate again, be stirred to and dissolve completely, in solution, ferric ion concentration is 4.6g/L, adds the pH to 8.0 of appropriate anhydrous sodium acetate regulation system.Then put into reactor, be airtightly heated to 200 DEG C, and be incubated 12 hours, cool to room temperature, be separated 2 ~ 3 times with ethanol purge, after solids vacuumize, namely obtain product.
According to the field emission scanning electron microscope image of the present embodiment product in Fig. 1, the product of gained is 150nm monodisperse colloid particle.From the transmission electron microscope picture of the single particle in Fig. 1 lower right corner, particle kernel is by a lot of once nanocrystalline secondary aggregates formed, and the contrast of particle surface 10nm thick layer is starkly lower than inside particles contrast, illustrates that particle surface is by Coated with Organic Matter.According to the X ray diffracting spectrum of product in Fig. 2 in 2 θ=18.3,30.0,35.4,43.0,53.3, the diffraction maximum of 56.9 and 62.5 ° and the JCPDS89-0688 card of tri-iron tetroxide are in (111), (220), (311), (400), (422), the diffraction maximum of (511) and (440) crystal face overlaps completely can prove that the inorganic kernel of gained is tri-iron tetroxide.Fig. 3 is the infrared spectrogram of products therefrom, at 577cm
-1place is the absworption peak of tri-iron tetroxide, 3425 and 1083cm
-1place is the hydroxyl peak in glucosan derivative, 1652,1423 and 1291cm
-1for the characteristic peak of polyvinylpyrrolidone in product.Fig. 4 is the thermogravimetric analysis collection of illustrative plates of products therefrom, and the inorganic phase component of products therefrom is probably 85.86wt%.From Fig. 5, the saturation magnetization of products therefrom when 300K is 53.5emug
-1, coercive force is close to 0, and the saturation magnetization when 10K is 67.2emug
-1, coercive force is 217Oe.Can find that the field cold curve of cold-peace null field of products therefrom overlaps near 250K by Fig. 6.Can prove that products therefrom at room temperature has superparamagnetism.
Embodiment 2
Glucosan derivative gluconic acid and polyvinylpyrrolidone are added in ethylene glycol and be mixed with uniform mixed solution, gluconic acid concentration is 9g/L or 13.3g/L, and polyvinylpyrrolidone concentration is 100g/L.Then add in mixed solution by ferric chloride hexahydrate, be stirred to and dissolve completely, in solution, the concentration of ferric ion is 4.6g/L.Finally add NaOH and regulate pH to 9.0.Then put into reactor, be airtightly heated to 220 DEG C, and be incubated 12 hours, then cool to room temperature, be separated 2 ~ 3 times with ethanol purge, after solids vacuumize, namely obtain product.The ESEM pattern of 9g/L and 12g/L concentration of glucose products therefrom is as shown in Fig. 7 (9g/L) and Fig. 8 (13.3g/L), and particle size is respectively 100nm, 220nm.
Embodiment 3
Tannic acid and polyvinylpyrrolidone are added in ethylene glycol and be mixed with uniform mixed solution, tannic acid concentration is 3.33g/L, and polyvinylpyrrolidone concentration is 400g/L.Then add in mixed solution by ferric chloride hexahydrate, be stirred to and dissolve completely, in solution, the concentration of ferric ion is 4.1g/L or 8.6g/L.Finally add anhydrous sodium acetate and regulate pH to 9.0.Then put into reactor, be airtightly heated to 200 DEG C, and be incubated 24 hours, then cool to room temperature, be separated 2 ~ 3 times with ethanol purge, after solids vacuumize, namely obtain product.The ESEM pattern of 4.1g/L and 8.6g/L ferric ion concentration products therefrom is as shown in Fig. 9 (4.1g/L) and Figure 10 (8.6g/L), and particle size is respectively 90nm and 230nm.
Embodiment 4
By tannic acid, it is be mixed with uniform mixed solution in the ethylene glycol of 2:1 and the solution of tirethylene glycol that gallic acid and polyvinylpyrrolidone join volume ratio, tannic acid concentration is 2.22g/L, and the concentration of gallic acid is 1.11g/L, and polyvinylpyrrolidone concentration is 100g/L.Then add in mixed solution by ferric sulfate, be stirred to and dissolve completely, in solution, the concentration of ferric ion is 4.6g/L, finally adds anhydrous sodium acetate and regulates pH to 10.0.Then put into reactor, be airtightly heated to 200 DEG C, and be incubated 6 hours or 48 hours, then cool to room temperature, be separated 2 ~ 3 times with ethanol purge, after solids vacuumize, namely obtain product.The ESEM pattern of insulation 6h and 48h products therefrom is as shown in Figure 11 (6h) and Figure 12 (48h).
Embodiment 5
Tannic acid and polyvinylpyrrolidone are added in ethylene glycol and be configured to uniform mixed solution, tannic acid concentration is 0.33g/L, and the concentration of polyvinylpyrrolidone is 16.7g/L.Then will enter ferric chloride hexahydrate adds in mixed solution, is stirred to and dissolves completely, the concentration 1.12g/L of ferric ion in solution.Finally add anhydrous sodium acetate and regulate pH to 9.0.Then put into reactor, be airtightly heated to 200 DEG C, and be incubated 24 hours, then cool to room temperature, be separated 2 ~ 3 times with ethanol purge, after solids vacuumize, namely obtain product.The ESEM pattern of products therefrom as shown in figure 13.
Embodiment 6
Above-described embodiment 1-4 products therefrom can be dispersed in different organic solvents, such as dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetic acid, alkanols, carrene etc., then pour in the sample bottle of 5ml, its variable color light spectrogram in different solvents is respectively as shown in Figure 14-Figure 20.
Embodiment 7
Be scattered in by product obtained by above-described embodiment 1-4 in 20% water-80% ethanolic solution, changing the size of externally-applied magnetic field, is 0M, 0.05M and 0.1M at sodium chloride concentration, pH value be 3.0,7.0 with 10.0 time can keep the scope of the same variable color.As shown in Figure 21-Figure 26, variable color liquid prepared by this product is described by the impact of ionic strength and pH value, proving that this product is is the photon crystal material of repulsive force with sterically hindered.
Reactor in above-described embodiment can be polytetrafluoroethylene stainless steel cauldron, or other can the reactor of heat resisting and pressure resisting.
Embodiment 8
The monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles that the present embodiment provides, be a kind of monodisperse, ultra paramagnetic nanometer crystal druse particle assembled by ferriferrous oxide nano crystalline substance, this particle surface is coated by polyvinylpyrrolidone.
Claims (3)
1. the preparation method of a monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles, it is characterized in that this compound particle is a kind of monodisperse, ultra paramagnetic nanometer crystal druse particle assembled by ferriferrous oxide nano crystalline substance, its surface is coated by polyvinylpyrrolidone, and the method comprises the following steps:
(1) polyol and polyvinylpyrrolidone are added in ethylene glycol or tirethylene glycol and be mixed with uniform mixed solution, described polyol, the concentration of polyvinylpyrrolidone are respectively (0.33 ~ 13.3) g/L, (16.7 ~ 400) g/L;
(2) add in mixed solution by trivalent iron salt, be stirred to and dissolve completely, in solution, ferric ion concentration is (1.12 ~ 8.6) g/L, and adjust ph is to 8.0-10.0;
(3) solution of step (2) is put into reactor, be airtightly heated to 180-240 DEG C, and be incubated 6-48 hour, obtain monodispersed super-paramagnetic ferriferrous oxide/polyvinylpyrrolidone nanometer crystal druse colloid Core-shell Composite Particles;
Described polyol is one in glucose, tannic acid, gallic acid, gluconic acid or mixture.
2. preparation method according to claim 1, is characterized in that described trivalent iron salt is one in iron chloride hexahydrate, ferric trichloride, ferric sulfate, ferric sulfate hydrate or mixture.
3. preparation method according to claim 1, is characterized in that with the one in sodium acetate, potassium acetate, NaOH, potassium hydroxide or mixture, the pH value described in regulating step (2).
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