CN103342393A - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 239000002159 nanocrystal Substances 0.000 title abstract 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 29
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- 229940074391 gallic acid Drugs 0.000 claims description 6
- 235000004515 gallic acid Nutrition 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 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
- 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
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 21
- 239000004038 photonic crystal Substances 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000003086 colorant Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 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
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- 239000000243 solution Substances 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 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
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
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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 the magnetic Nano material preparation field, particularly relate to a kind of monodispersed super-paramagnetic ferriferrous oxide/polyvinylpyrrolidone nanometer crystal druse colloid nucleocapsid composite particles and preparation method thereof.
Background technology
The magnetic responsiveness photonic crystal refers to a kind of responsiveness photon crystal material that the color of material can be controlled by the variation of externally-applied magnetic field intensity.At sensing, technique of display, speculum, civil area such as energy-conservation purposes is quite widely arranged.Be that the research of the magnetic responsiveness photonic crystal of primitive has obtained major progress with the Z 250 sub-micron ball at present.U.S.'s " advanced material " magazine (Adv.Mater.2001, the 13rd volume, 1681 pages) reported a kind of PS colloid micro ball that contains 17% ferritic super paramagnetic, but the content of magnetic component is too low in the colloid primitive, can not realize full spectrum variable color so the spacing of particle variable range is less.Germany " applied chemistry " magazine (Angew.Chem.Int.Edit.2007, the 46th volume, 7428 pages) reported that polyacrylic acid coats by the brilliant super paramagnetic secondary aggregate of forming of ferriferrous oxide nano, in the time of in being scattered in the aqueous solution, under the effect of externally-applied magnetic field, the one dimension 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 the aqueous solution, limit the range of application of magnetic photonic crystal, how producing stronger repulsive force in the more weak non-aqueous solvent of polarity becomes an obstacle widening the magnetic photonic crystal range of application.U.S.'s " advanced material " magazine (Adv.Mater.2009, the 21st volume, 4259 pages) reported a kind of Z 250 sub-micron ball of coated with silica, the affinity of dependence silicon-dioxide and alkanol can be enough at alkanols (methyl alcohol, ethanol, ethylene glycol, glycerine etc.) disperse in the solvent, and can rely on silicon-dioxide with surface charge from this sub-micron ball can variable color the alkanol solvent under the effect of externally-applied magnetic field.But above all methods of reporting all are to rely on electrostatic repulsion to construct photonic crystal as the long-range repulsive force, and electrostatic repulsion is a kind of solvent polarity that very easily is subjected to, the reactive force of ionic strength and the influence of pH value.This has also just limited existing magnetic photonic crystal can only combine to prepare optics with hydrophilic non-ionic resin, and make its performance reduction with depositing the influence (such as the change of ionic strength and pH value) that very easily is subjected to outside atmosphere in the process in building-up process, the range of application that has limited existing photon crystal material greatly improves its permanent stability.The present invention is directed to above problem, prepared and produce sterically hindered repulsive force with the polyvinyl pyrrolidone polymers layer and replace electrostatic repulsion to come the magnetic nano-particle of balance externally-applied magnetic field.Making this particle can both better disperse and add in the solvent of opposed polarity has wideer color change interval under the action of a magnetic field, and its color change interval is not subjected to the influence 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 the long-range repulsive force at existing magnetic photonic crystal, significantly descend thereby the operating distance of repulsive force reduces with polarity of solvent and very easily be subjected to the shortcoming of the influence of ionic strength and pH value, provide a kind of preparation method of sterically hindered stable super paramagnetic colloidal particle to solve the problems referred to above.
The present invention solves its technical problem and adopts following technical scheme:
Monodispersed super paramagnetic nano druse colloid nucleocapsid composite particles provided by the invention is a kind of by the brilliant monodisperse, ultra paramagnetic nanometer crystal druse particle that forms of assembling of ferriferrous oxide nano, and this particle surface is coated by polyvinylpyrrolidone.
Monodispersed super paramagnetic nano druse colloid nucleocapsid composite particles provided by the invention, its preparation method are to adopt the method that may further comprise the steps:
(1) will be mixed with uniform mixing solutions in polyol and the polyvinylpyrrolidone adding polyvalent alcohol, the concentration of described polyol, polyvinylpyrrolidone is respectively (0.33～13.3) g/L, (16.7～400) g/L;
(2) trivalent iron salt is added in the mixing solutions, be stirred to dissolving fully, ferric ion concentration is (1.12～8.6) g/L in the solution, regulates the pH value to 8.0-10.0;
(3) solution of step (2) is put into the tetrafluoroethylene stainless steel cauldron, airtightly be heated to 180-240 ℃, and insulation got final product in 6-48 hour, obtain monodispersed super-paramagnetic ferriferrous oxide/polyvinylpyrrolidone nanometer crystal druse colloid nucleocapsid composite particles.
Described polyol can be a kind of or mixture in glucose, Weibull, the gallic acid.
Described polyol can be the derivative of glucose, Weibull, gallic acid.
Described polyvalent alcohol can be ethylene glycol or tirethylene glycol.
Described trivalent iron salt can be a kind of in iron chloride hexahydrate, iron trichloride, ferric sulfate, the ferric sulfate hydrate, or mixture.
The present invention can use a kind of or mixture in sodium-acetate, Potassium ethanoate, sodium hydroxide, the potassium hydroxide, the described pH value of regulating step (2).
The present invention compared with prior art has following major advantage:
One replaces electrostatic repulsion to construct the magnetic responsiveness photonic crystal with space bit resistance type repulsive force.The present invention mainly is by adopting polyol (as: glucose, Weibull or gallic acid or their mixture; ) as nanocrystalline inhibitor once, polyvinylpyrrolidone is as the dispersion agent of nanometer crystal druse.
Its two, the prepared product of the present invention have the height chemistry and colloidal stability.Rely on the polyvinylpyrrolidone space bit resistance layer on surface, improved the dispersion stabilization of magnetic particle in all kinds of SOLVENTS (water, dimethyl sulfoxide (DMSO), dimethyl formamide, acetic acid, alkanol, methylene dichloride etc.).
Its three, magnetic control of the present invention is assembled out the photonic crystal of different colours, prepared product can make the metachrosis of magnetic photonic crystal not be subjected to the influence of solvent polarity.Because the surface is coated with the polymer layer of polyvinylpyrrolidone, and sterically hindered reactive force comes from the swelling ability of product surface polyvinylpyrrolidone and different organic solvents, and is relevant to the solvating ability of polyvinylpyrrolidone with solvent.Also make this variable color liquid in different solvents, by applying externally-applied magnetic field, thereby show wideer color change interval.
Its four, the prepared product of the present invention can improve magnetic photonic crystal for the resistivity of ionic strength and pH value.
Description of drawings
Fig. 1 is the field emission scanning electron microscope image of product in the embodiments of the invention 1.
Fig. 2 is the X ray diffracting spectrum of product in the embodiments of the invention 1.
Fig. 3 is the infrared spectrogram of product in the embodiments of the invention 1.
Fig. 4 is the thermogravimetric analysis figure of product in the embodiments of the invention 1.
Fig. 5 is the mangneto loop line figure of product in the embodiments of the invention 1.
Fig. 6 is the cold graphic representation of field cold-peace null field of product in the embodiments of the invention 1.
Fig. 7 is the scanning electron microscope diagram of product among the embodiment 2.
Fig. 8 is the scanning electron microscope diagram of product among the embodiment 2.
Fig. 9 is the scanning electron microscope diagram of product among the embodiment 3.
Figure 10 is the scanning electron microscope diagram of product among the embodiment 3.
Figure 11 is the scanning electron microscope diagram of product among the embodiment 4.
Figure 12 is the scanning electron microscope diagram of product among the embodiment 4.
Figure 13 is the scanning electron microscope diagram of product among the embodiment 5.
Figure 14 is the variable color light spectrogram of product in dimethyl formamide (DMF) solvent among the embodiment 1.
Figure 15 is the variable color light spectrogram of product in ethanol among the embodiment 1.
Figure 16 is the variable color light spectrogram of product in methylene dichloride (DCM) among the embodiment 1.
Figure 17 is the variable color light spectrogram of product in dimethyl sulfoxide (DMSO) (DMSO) among the embodiment 1.
Figure 18 is the variable color light spectrogram of product in acetic acid solvent among the embodiment 1.
Figure 19 be among the 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 among the embodiment 1.
Figure 21 is the variable color light spectrogram of product among the embodiment 1 when sodium chloride concentration is 0M in 20% water-80% ethanolic soln.
Figure 22 is the variable color light spectrogram of product among the embodiment 1 when sodium chloride concentration is 0.05M in 20% water-80% ethanolic soln.
Figure 23 is the variable color light spectrogram of product among the embodiment 1 when sodium chloride concentration is 0.1M in 20% water-80% ethanolic soln.
Figure 24 is 3.0 o'clock variable color light spectrogram for product pH in 20% water-80% ethanolic soln among the embodiment 1.
Figure 25 is 7.0 o'clock variable color light spectrogram for product pH in 20% water-80% ethanolic soln among the embodiment 1.
Figure 26 is 10.0 o'clock variable color light spectrogram for product pH in 20% water-80% ethanolic soln among the embodiment 1.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but do not limit the present invention.
Embodiment 1
To be mixed with uniform mixing solutions in glucose and the polyvinylpyrrolidone adding ethylene glycol, glucose concn is 10g/L, and polyvinylpyrrolidone concentration is 100g/L.Six Ferric Chloride Hydrateds are added in the mixing solutions again, be stirred to dissolving fully, ferric ion concentration is 4.6g/L in the solution, adds the pH to 8.0 of an amount of sodium acetate, anhydrous regulation system.Put into reactor then, airtightly be heated to 200 ℃, and be incubated 12 hours, cool to room temperature cleans with ethanol and to separate 2～3 times, namely obtains product after the solids vacuum-drying.
According to the field emission scanning electron microscope image of present embodiment product among Fig. 1 as can be known, the product of gained is the single dispersoid particle of 150nm.By the transmission electron microscope picture of the single particle in Fig. 1 lower right corner as seen, the particle kernel is by a lot of once nanocrystalline secondary aggregates of forming, and the contrast of particle surface 10nm thick layer is starkly lower than the inner contrast of particle, illustrates that particle surface is coated by organism.According to the X ray diffracting spectrum of product among Fig. 2 in 2 θ=18.3,30.0,35.4,43.0,53.3,56.9 and the JCPDS89-0688 card of 62.5 ° diffraction peak and Z 250 is in (111), (220), (311), (400), (422), to overlap the inorganic kernel that can prove gained fully be Z 250 to the diffraction peak of (511) and (440) crystal face.Fig. 3 is the infrared spectrogram of products therefrom, at 577cm
-1The place is the absorption peak of Z 250,3425 and 1083cm
-1The place is the hydroxyl peak in the glucose-derivative, 1652,1423 and 1291cm
-1Characteristic peak for polyvinylpyrrolidone in the product.Fig. 4 is the thermogravimetric analysis collection of illustrative plates of products therefrom, and the inorganic phase component of products therefrom probably is 85.86wt%.By Fig. 5 as can be known, 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.The field cold curve of cold-peace null field that can be found products therefrom by Fig. 6 overlaps near 250K.Can prove that products therefrom at room temperature has superparamagnetism.
Embodiment 2
To be mixed with uniform mixing solutions in glucose-derivative gluconic acid and the polyvinylpyrrolidone adding ethylene glycol, gluconic acid concentration is 9g/L or 13.3g/L, and polyvinylpyrrolidone concentration is 100g/L.Then six Ferric Chloride Hydrateds are added in the mixing solutions, be stirred to dissolving fully, the concentration of ferric ion is 4.6g/L in the solution.Add sodium hydroxide at last and regulate pH to 9.0.Put into reactor then, airtightly be heated to 220 ℃, and be incubated 12 hours, cool to room temperature then cleans with ethanol and to separate 2～3 times, namely obtains product after the solids vacuum-drying.The scanning electron microscope pattern of 9g/L and 12g/L glucose concn products therefrom is shown in Fig. 7 (9g/L) and Fig. 8 (13.3g/L), and size is respectively 100nm, 220nm.
Embodiment 3
To be mixed with uniform mixing solutions in Weibull and the polyvinylpyrrolidone adding ethylene glycol, Weibull concentration is 3.33g/L, and polyvinylpyrrolidone concentration is 400g/L.Then six Ferric Chloride Hydrateds are added in the mixing solutions, be stirred to dissolving fully, the concentration of ferric ion is 4.1g/L or 8.6g/L in the solution.Add sodium acetate, anhydrous at last and regulate pH to 9.0.Put into reactor then, airtightly be heated to 200 ℃, and be incubated 24 hours, cool to room temperature then cleans with ethanol and to separate 2～3 times, namely obtains product after the solids vacuum-drying.4.1g/L and the scanning electron microscope pattern of 8.6g/L ferric ion concentration products therefrom is shown in Fig. 9 (4.1g/L) and Figure 10 (8.6g/L), size is respectively 90nm and 230nm.
Embodiment 4
With Weibull, gallic acid and polyvinylpyrrolidone join in the solution of ethylene glycol that volume ratio is 2:1 and tirethylene glycol and are mixed with uniform mixing solutions, Weibull concentration is 2.22g/L, and the concentration of gallic acid is 1.11g/L, and polyvinylpyrrolidone concentration is 100g/L.Then ferric sulfate is added in the mixing solutions, be stirred to dissolving fully, the concentration of ferric ion is 4.6g/L in the solution, adds sodium acetate, anhydrous at last and regulates pH to 10.0.Put into reactor then, airtightly be heated to 200 ℃, and be incubated 6 hours or 48 hours, cool to room temperature then cleans with ethanol and to separate 2～3 times, namely obtains product after the solids vacuum-drying.The scanning electron microscope pattern of insulation 6h and 48h products therefrom is shown in Figure 11 (6h) and Figure 12 (48h).
Embodiment 5
To be configured to uniform mixing solutions in Weibull and the polyvinylpyrrolidone adding ethylene glycol, Weibull concentration is 0.33g/L, and the concentration of polyvinylpyrrolidone is 16.7g/L.To go into six Ferric Chloride Hydrateds then and add in the mixing solutions, be stirred to dissolving fully, the concentration 1.12g/L of ferric ion in the solution.Add sodium acetate, anhydrous at last and regulate pH to 9.0.Put into reactor then, airtightly be heated to 200 ℃, and be incubated 24 hours, cool to room temperature then cleans with ethanol and to separate 2～3 times, namely obtains product after the solids vacuum-drying.The scanning electron microscope pattern of products therefrom as shown in figure 13.
Embodiment 6
Above-described embodiment 1-4 products therefrom can be dispersed in the different organic solvents, for example dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetic acid, alkanols, methylene dichloride etc., pour into then in the sample bottle of 5ml, its variable color light spectrogram in different solvents is respectively as Figure 14-shown in Figure 20.
Embodiment 7
The prepared product of above-described embodiment 1-4 being scattered in 20% water-80% ethanolic soln, changing the size of externally-applied magnetic field, is 0M at sodium chloride concentration, 0.05M and 0.1M, the pH value be 3.0,7.0 with the scope that can both keep the same variable color at 10.0 o'clock.As Figure 21-shown in Figure 26, illustrate that the prepared variable color liquid of this product is not subjected to the influence of ionic strength and pH value, prove that this product is is the photon crystal material of repulsive force with sterically hindered.
Reactor in above-described embodiment can be the tetrafluoroethylene stainless steel cauldron, or the reactor that other can heat resisting and pressure resisting.
Embodiment 8
The monodispersed super paramagnetic nano druse colloid nucleocapsid composite particles that present embodiment provides is a kind of by the brilliant monodisperse, ultra paramagnetic nanometer crystal druse particle that forms of assembling of ferriferrous oxide nano, and this particle surface is coated by polyvinylpyrrolidone.
Claims (6)
1. a monodispersed super paramagnetic nano druse colloid nucleocapsid composite particles is characterized in that a kind of monodisperse, ultra paramagnetic nanometer crystal druse particle that is formed by the brilliant gathering of ferriferrous oxide nano, and this particle surface is coated by polyvinylpyrrolidone.
2. the preparation method of a monodispersed super paramagnetic nano druse colloid nucleocapsid composite particles is characterized in that adopting the method that may further comprise the steps:
(1) will be mixed with uniform mixing solutions in polyol and the polyvinylpyrrolidone adding polyvalent alcohol, the concentration of described polyol, polyvinylpyrrolidone is respectively (0.33～13.3) g/L, (16.7～400) g/L;
(2) trivalent iron salt is added in the mixing solutions, be stirred to dissolving fully, ferric ion concentration is (1.12～8.6) g/L in the solution, regulates the pH value to 8.0-10.0;
(3) solution of step (2) is put into reactor, airtightly be heated to 180-240 ℃, and insulation 6-48 hour, monodispersed super-paramagnetic ferriferrous oxide/polyvinylpyrrolidone nanometer crystal druse colloid nucleocapsid composite particles obtained.
3. preparation method according to claim 2 is characterized in that described polyol is a kind of or mixture in glucose, Weibull, gallic acid and their derivative thereof.
4. preparation method according to claim 2 is characterized in that described polyvalent alcohol is ethylene glycol or tirethylene glycol.
5. preparation method according to claim 2 is characterized in that described trivalent iron salt is a kind of or mixture in iron chloride hexahydrate, iron trichloride, ferric sulfate, the ferric sulfate hydrate.
6. preparation method according to claim 2 is characterized in that with a kind of or mixture in sodium-acetate, Potassium ethanoate, sodium hydroxide, the potassium hydroxide, the described pH value of regulating step (2).
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