CN101752047B - Three-dimensional ordered inorganic magnetism macroporous material and preparation method thereof - Google Patents
Three-dimensional ordered inorganic magnetism macroporous material and preparation method thereof Download PDFInfo
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- CN101752047B CN101752047B CN200810204112A CN200810204112A CN101752047B CN 101752047 B CN101752047 B CN 101752047B CN 200810204112 A CN200810204112 A CN 200810204112A CN 200810204112 A CN200810204112 A CN 200810204112A CN 101752047 B CN101752047 B CN 101752047B
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Abstract
The invention relates to a three-dimensional ordered inorganic magnetism macroporous material and preparation method thereof. The preparation method comprises the following steps: dispersing magnetic nanometer particles and high-molecular micro-balloons into solution, simultaneously depositing the magnetic nanometer particles and the high-molecular micro-balloons through the solution volatilization self-assembly process, filling the magnetic nanometer particles into gaps formed by orderly arranging the high-molecular micro-balloons, then filling inorganic oxide sol in residual voids of high-molecular micro-balloon/magnetic nanometer particle composite materials through a nanometer casting method, filling inorganic oxide into voids formed by the high-molecular micro-balloons through further in-situ condensation under the air atmosphere, thereby fixing an ordered composite structure, and finally, three-dimensional ordered macroporous material is obtained by removing the high-molecular micro-balloons by calcining under nitrogen atmosphere. The magnetism macroporous material has the advantages of stronger magnetic response, higher stability and wide application in aspects of biological separation, medicament carrying, catalytic load and the like and has a three-dimensionally communicated and ordered macro pore.
Description
Technical field:
The invention belongs to nano composite material and field of nanometer technology, be specifically related to a kind of have inorganic magnetic three-dimensional ordered macro-porous material and synthetic method thereof.
Technical background:
In recent years, three-dimensional ordered macroporous material is because the particularity of its structure becomes a kind of advanced composite material (ACM) with wide application prospect.Adopt the inorganic magnetic three-dimensional ordered macro-porous material of magnetisable material doping wall it to be with a wide range of applications at aspects such as bio-separation, medicament transport, catalysis loads because it has the architectural characteristic that magnetic responsiveness that magnetic material has and three-dimensional ordered macroporous material have.
So far, for the synthetic existing certain report of magnetism macroporous material with three-dimensional order, but in the existing report, not only synthesis step is various, and needs hydrogen reducing, makes building-up process extremely complicated; Simultaneously, its wall consist of metal, be difficult to further modification, limited the application of material; Wherein used magnetic material is metals such as Ni, Co, and biocompatibility is poor, is difficult to be applicable to (Yan, H.W. in the biotechnology; Blanford, C.F.; Holland, B.T.; Parent, M.; Smyrl, W.H.Stein, A.Adv.Mater.1999,11,1003.Krivorotov, I.N.; Yan, H.W.; Dahlberg, E.D.; Stein, A.J.Magnet.Magnet.Mater.2001,226-230,1800.).
Recently, though there is report to propose, through the magnetic of giving material at the silane derivative of the synthetic three-dimensional ordered macroporous material doped poly-ferrocene of silicon dioxide.Yet its synthesis material is expensive, and synthetic method is complicated, and raw material has bigger toxicity, is not suitable for the application of living things system equally.The characteristics of the magnetic responsiveness difference that these methods of while all face.Up to the present, not about having strong magnetic responsiveness, report (Galloro, J. with simple and easy synthetic aspect of the adaptive inorganic magnetic three-dimensional ordered macro-porous material of higher biological; Ginzburg, M.; Miguez, H.; Yang, S.M.; Coombs, N.; Safa-Sefat, A.; Greedan, J.E.; Manners, I.; Ozin, G.A.Adv.Funct.Mater.2002,12,382.).
Summary of the invention:
The object of the present invention is to provide a kind of inorganic magnetism macroporous material and preparation method thereof with three-dimensional order.
Inorganic magnetism macroporous material with three-dimensional order provided by the present invention; Be a kind of be masterplate with the polymer microsphere, utilize solvent evaporates to induce self assembly (EISA) technology and " nanometer casting (Nanocasting) " technology that magnetic nano-particle and inorganic oxide sol are packed in the colloid crystalline substance that polymer microsphere is arranged in.And then remove polymer microsphere through calcining and form inorganic magnetic three-dimensional ordered macro-porous material.In concrete synthesizing, co-precipitation magnetic nano-particle and polymer microsphere in the solvent of water or alcohols utilize solution evaporation to induce self assembly (EISA) to make magnetic nano-particle be filled in the space of polymer microsphere array; Utilize the technology of " nanometer casting (Nanocasting) " inorganic oxide sol to be inserted in the remaining space in space then; Further hydrolytic crosslinking coated magnetic nanoparticle through inorganic oxide sol forms three-dimensional network, removes polymer microsphere through high-temperature calcination again, just obtains the inorganic magnetism macroporous material of three-dimensional order.Size, the cavity size of the magnetic nano-particle in the synthetic resulting three-dimensional order magnetism macroporous material; The intercommunicating pore size is all adjustable continuously; Scope is following: the size of magnetic nano-particle is at 3nm～20nm, and cavity size is at 100nm～2 μ m, and the intercommunicating pore aperture is at 10nm～50nm.
Among the present invention, the inorganic magnetic nano particle consist of Fe
3O
4, γ-Fe
2O
3, NiFe
2O
4, CuFe
2O
4, iron, nickel, a kind of in the cobalt etc.
Among the present invention, when polymer microsphere and magnetic nanoparticle co-precipitation, use be that solvent evaporates is induced self-assembling technique (EISA).Concrete steps are following: inorganic magnetic nano particle and polymer microsphere are dispersed in the solvent of water or the mixing of pure water, place at a certain temperature, dried solvent volatilizees.Wherein, used polymer microsphere is one or more in polystyrene microsphere, the poly (methyl methacrylate) micro-sphere; Employed solvent is the mixture of water or water and alkylol, and alkylol wherein is one or more in methyl alcohol, ethanol or the isopropyl alcohol.
Employed among the present invention " nanometer casting (Nanocasting) " technology; Its concrete steps are following: will volatilize solvent; The polymer microsphere array that is packed into the inorganic magnetic nano particle immerses in the colloidal sol of inorganic oxide precursor; Take out after after a while and dry, under nitrogen atmosphere, calcine after the repeated multiple times and get final product.
In synthetic, utilize the inorganic oxide sol hydrolytic crosslinking, parcel inorganic magnetic nano particle is filled the space of full polymer microsphere array simultaneously, is removed and obtains inorganic magnetic three-dimensional ordered macro-porous material through calcining back polymer microsphere.Inorganic oxide wherein is one or more in silicon dioxide, titanium dioxide, the zirconium dioxide.
Related inorganic magnetism macroporous material among the present invention with three-dimensional order; The material of being reported before different; It has the water-wetted surface that is easy to modify, very high magnetic response, the aperture of the cavity volume of homogeneous, three-dimensional order and connection; Its wall consists of inorganic oxide, has certain biocompatibility.In the synthetic method that the present invention reported, made full use of the characteristic of magnetic material; Employing magnetic separates, and has used the brilliant method of co-precipitation colloid simultaneously, and it is high to have rapid simple, that raw material is prone to, the synthetic material purity of synthetic method; The characteristics that homogeneity is good are particularly suitable for large-scale production.Simultaneously, because characteristics such as the aperture of its strong magnetic responsiveness that has, homogeneous, excellent biological compatibility have important application prospects in fields such as bio-separation, medicine delivery, catalysis loads.
Description of drawings
Figure 1A, 1B are the electron scanning micrograph of inorganic magnetic three-dimensional ordered macro-porous material.
Fig. 1 C, 1D are three-dimensional order magnetism macroporous material transmission electron microscope photo.
Fig. 1 E is a three-dimensional order magnetism macroporous material high resolution transmission electron microscopy photo, wherein is the SEAD photo.
Embodiment:
Embodiment 1:
(1) with the Fe of 0.2g superparamagnetism 10nm
3O
4The ultrasonic 20ml 2M HNO that is distributed to of nano particle
31～2min carries out preliminary treatment in the solution, fully cleans magnetic nano-particle with deionized water, again with its ultrasonic again 4.4g natrium citricum that is distributed to, in the mixed solution of 20ml deionized water.Use the magnet separated product at last, and it is distributed to obtain stable dispersion liquid among the deionized water 5ml subsequent use.
(2) polystyrene sphere with 10g 380nm is distributed in the 300g deionized water, gets this solution of 5g and above-mentioned Fe again
3O
4Nano-particle solution is mixed, and then mixed liquor is put into 35 ℃ of baking ovens and dries.Put into 80 ℃ of baking oven 24h after the oven dry.The gained solid is immersed in the mixed solution of 0.9gTEOS, 0.1g 2M HCl, 8g ethanol and 2g deionized water, volatilizes until solution.Resulting solid is put into the crucible of 5ml.Crucible is put in the tube furnace, and the control heating rate is that 2 ℃/min calcines 6h down in 400 ℃ under nitrogen atmosphere.Just obtain required sample after the taking-up.
Embodiment 2:
(1) with γ-Fe of 0.2g superparamagnetism 10nm
2O
3The ultrasonic 20ml 2M HNO that is distributed to of nano particle
31～2min carries out preliminary treatment in the solution, fully cleans magnetic nano-particle with deionized water, again with its ultrasonic again 4.4g natrium citricum that is distributed to, in the mixed solution of 20ml deionized water.Use the magnet separated product at last, and it is distributed to obtain stable dispersion liquid among the deionized water 5ml subsequent use.
(2) polystyrene sphere with 10g 380nm is distributed in the 300g deionized water, gets this solution of 5g again and mixes with above-mentioned γ-Fe2O3 nano-particle solution, then mixed liquor is put into 35 ℃ of baking ovens and dries.Put into 80 ℃ of baking oven 24h after the oven dry.The gained solid is immersed in the mixed solution of 0.9gTEOS, 0.1g 2M HCl, 8g ethanol and 2g deionized water, volatilizes until solution.Resulting solid is put into the crucible of 5ml.Crucible is put in the tube furnace, and the control heating rate is that 2 ℃/min is in 400 ℃ of following calcination 6h under nitrogen atmosphere.Just obtain required sample after the taking-up.
Embodiment 3:
(1) with the Fe of 0.2g superparamagnetism 10nm
3O
4The ultrasonic 20ml 2M HNO that is distributed to of nano particle
31～2min carries out preliminary treatment in the solution, fully cleans magnetic nano-particle with deionized water, again with its ultrasonic again 4.4g natrium citricum that is distributed to, in the mixed solution of 20ml deionized water.Use the magnet separated product at last, and it is distributed to obtain stable dispersion liquid among the deionized water 5ml subsequent use.
(2) polystyrene sphere with 10g 1 μ m is distributed in the 300g deionized water, gets this solution of 5g and above-mentioned Fe again
3O
4Nano-particle solution is mixed, and then mixed liquor is put into 35 ℃ of baking ovens and dries.Put into 80 ℃ of baking oven 24h after the oven dry.The gained solid is immersed in the mixed solution of 0.9gTEOS, 0.1g 2M HCl, 8g ethanol and 2g deionized water, volatilizes until solution.Resulting solid is put into the crucible of 5ml.Crucible is put in the tube furnace, and the control heating rate is that 2 ℃/min is in 400 ℃ of following calcination 6h under nitrogen atmosphere.Be the gained sample after the taking-up.
Embodiment 4:
(1) with the Fe of 0.2g superparamagnetism 10nm
3O
41～2min carries out preliminary treatment in the ultrasonic 20ml of the being distributed to 2M of the nano particle HNO3 solution, fully cleans magnetic nano-particle with deionized water, again with its ultrasonic again 4.4g natrium citricum that is distributed to, in the mixed solution of 20ml deionized water.Use the magnet separated product at last, and it is distributed to obtain stable dispersion liquid among the deionized water 5ml subsequent use.
(2) polystyrene sphere with 10g 380nm is distributed in the 300g deionized water, gets this solution of 5g and above-mentioned Fe again
3O
4Nano-particle solution is mixed, and then mixed liquor is put into 35 ℃ of baking ovens and dries.Put into 100 ℃ of baking oven 24h after the oven dry.Oven dry back gained solid is immersed in 3h in the mixed solution of 0.9gTEOS, 0.1g 2M HCl, 8g ethanol and 2g deionized water, volatilizes until solution.Resulting solid is put into the crucible of 5ml.Crucible is put in the tube furnace, and the control heating rate is that 2 ℃/min is in 400 ℃ of following calcination 6h under nitrogen atmosphere.Be the gained sample after the taking-up.
Embodiment 5:
(1) with the Fe of 0.2g superparamagnetism 10nm
3O
4The ultrasonic 20ml 2M HNO that is distributed to of nano particle
31～2min carries out preliminary treatment in the solution, fully cleans magnetic nano-particle with deionized water, again with its ultrasonic again 4.4g natrium citricum that is distributed to, in the mixed solution of 20ml deionized water.Use the magnet separated product at last, and it is distributed to obtain stable dispersion liquid among the deionized water 5ml subsequent use.
(2) polystyrene sphere with 10g 380nm is distributed in the 300g deionized water, gets this solution of 5g and above-mentioned Fe again
3O
4Nano-particle solution is mixed, and then mixed liquor is put into 35 ℃ of baking ovens and dries.Put into 80 ℃ of baking oven 24h after the oven dry.The gained solid is immersed in the mixed solution of 0.9g iso-butyl titanate, 0.1g2M HCl, 8g ethanol and 2g deionized water, volatilizes until solution.Resulting solid is put into the crucible of 5ml.Crucible is put in the tube furnace, and the control heating rate is that 2 ℃/min is in 400 ℃ of following calcination 6h under nitrogen atmosphere.Be the gained sample after the taking-up.
Embodiment 6:
(1) with the Fe of 0.2g superparamagnetism 10nm
3O
4The ultrasonic 20ml 2M HNO that is distributed to of Nano microsphere
31～2min carries out preliminary treatment in the solution, fully cleans magnetic nano-particle with deionized water, again with its ultrasonic again 4.4g natrium citricum that is distributed to, in the mixed solution of 20ml deionized water.Use the magnet separated product at last, and it is distributed to obtain stable dispersion liquid among the deionized water 5ml subsequent use.
(2) the polymethylacrylic acid bead with 10g 480nm is distributed in the 300g deionized water, gets this solution of 5g and above-mentioned Fe again
3O
4Nano-particle solution is mixed, and then mixed liquor is put into 35 ℃ of baking ovens and dries.Put into 80 ℃ of baking oven 24h after the oven dry.The gained solid is immersed in the mixed solution of 0.9gTEOS, 0.1g 2M HCl, 8g ethanol and 2g deionized water, volatilizes until solution.Resulting solid is put into the crucible of 5ml.Crucible is put in the tube furnace, and the control heating rate is that 2 ℃/min is in 400 ℃ of following calcination 6h under nitrogen atmosphere.Be the gained sample after the taking-up.
Claims (6)
1. inorganic magnetic three-dimensional ordered macro-porous material; It is characterized in that said material wall is the composite material of unformed inorganic oxide and magnetic nano-particle; The size of the cavity of material is adjustable continuously between 100nm～2 μ m, and the modifiable surface of possess hydrophilic property; The hole of three-dimensional communication is adjustable continuously between 10nm～50nm.
2. according to the desired three-dimensional order magnetism macroporous material of claim 1, it is characterized in that the Fe that consists of as the magnetic nano-particle in the wall
3O
4, γ-Fe
2O
3, NiFe
2O
4, CuFe
2O
4, iron, nickel, one or more in the cobalt magnetisable material, the size of inorganic magnetic nano particle is between 3nm～20nm.
3. the preparation method of an inorganic magnetic three-dimensional ordered macro-porous material as claimed in claim 1; It is characterized in that it comprises following concrete synthesis step: co-precipitation magnetic nano-particle and polymer microsphere in the solvent of water or alcohols, utilize the solution evaporation self assembly to make magnetic nano-particle be filled in the space of polymer microsphere array; To volatilize solvent then; The polymer microsphere array that is packed into the inorganic magnetic nano particle immerses in the colloidal sol of inorganic oxide precursor; Take out after after a while and dry, calcining under nitrogen atmosphere after the repeated multiple times is to insert inorganic oxide sol in the remaining space in space; Fill through the further hydrolysis of inorganic oxide sol in the space of the array that the polymer microsphere of full three-dimensional order arranges; Remove the magnetism macroporous material that polymer microsphere just obtains three-dimensional order through high-temperature calcination again.
4. preparation method according to claim 3, when it is characterized in that being the co-precipitation of inorganic magnetic nano particle, the polymer microsphere of use is one or more in polystyrene microsphere, the poly (methyl methacrylate) micro-sphere; Employed solvent is water or alcohols; Alcohols wherein is one or more in methyl alcohol or ethanol or the isopropyl alcohol.
5. preparation method according to claim 3 is characterized in that inorganic oxide in the employed colloidal sol is one or more in silicon dioxide, titanium dioxide or the zirconium dioxide; Solvent in the said colloidal sol is the mixture of water or alkylol and water, and alkylol wherein is one or more in methyl alcohol or ethanol or the isopropyl alcohol.
6. preparation method according to claim 3; It is characterized in that being synthetic resulting three-dimensional order magnetism macroporous material in magnetic nano-particle size, macropore cavity size and intercommunicating pore aperture all adjustable continuously, scope is following: the magnetic nano-particle size is at 3nm～20nm; Cavity size is adjustable continuously between 100nm～2 μ m; The intercommunicating pore diameter is adjustable continuously between 10nm～50nm; Saidly continuously adjustablely be meant that in the material of processing, the size in cavity and hole is covered with in this scope.
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| CN104445438B (en) * | 2014-12-20 | 2016-08-31 | 邵锋 | A kind of preparation method of super-paramagnetic ferriferrous oxide composite magnetic mesoporous material |
| CN106350004B (en) * | 2016-08-25 | 2018-04-17 | 华东理工大学 | A kind of hollow composite wave-suction material of sandwich structure type and preparation method thereof |
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| US7105138B2 (en) * | 2003-11-21 | 2006-09-12 | Korea Research Institute Of Standards And Science | Macroporous perovskite manganese oxides with highly ordered nano-pores and method of preparing the same |
| CN101081302A (en) * | 2007-05-24 | 2007-12-05 | 上海交通大学 | Process for preparing original position of nanometer laminated composite material |
| CN101630556A (en) * | 2009-06-11 | 2010-01-20 | 复旦大学 | Inorganic magnetic three-dimensional ordered macro-porous material and preparation method thereof |
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| US7105138B2 (en) * | 2003-11-21 | 2006-09-12 | Korea Research Institute Of Standards And Science | Macroporous perovskite manganese oxides with highly ordered nano-pores and method of preparing the same |
| CN101081302A (en) * | 2007-05-24 | 2007-12-05 | 上海交通大学 | Process for preparing original position of nanometer laminated composite material |
| CN101630556A (en) * | 2009-06-11 | 2010-01-20 | 复旦大学 | Inorganic magnetic three-dimensional ordered macro-porous material and preparation method thereof |
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