CN106710773B - A kind of monodisperse magnetic porous silica microballoon and preparation method thereof - Google Patents
A kind of monodisperse magnetic porous silica microballoon and preparation method thereof Download PDFInfo
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- CN106710773B CN106710773B CN201611140789.6A CN201611140789A CN106710773B CN 106710773 B CN106710773 B CN 106710773B CN 201611140789 A CN201611140789 A CN 201611140789A CN 106710773 B CN106710773 B CN 106710773B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000004005 microsphere Substances 0.000 claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001566 austenite Inorganic materials 0.000 claims description 4
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- -1 Glycidol ester Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011806 microball Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910021426 porous silicon Inorganic materials 0.000 description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 9
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 7
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000007619 statistical method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001448 ferrous ion Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/342—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
-
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
This application discloses a kind of monodisperse magnetic porous silica microballoons and preparation method thereof.The preparation method of the monodisperse magnetic porous silica microballoon of the application is template, in-situ preparation magnetic Fe using monodisperse porous polymer microsphere3O4Particle, the sol gel of silicon source and magnetic Fe3O4Particle is oxidized to γ-Fe2O3, magnetic high-molecular-SiO 2 composite microsphere is formed, chelating polymer template is removed using calcining, obtains monodisperse porous magnetic silica microballoon.The preparation method simple process of the application, easy to operate, the monodisperse magnetic porous silica microballoon of preparation has many advantages, such as controllable uniform particle diameter, partial size and aperture, Kong Liantong, introduces that magnetic nano particle submethod is simple and magnetic stability.
Description
Technical field
It is porous more particularly to a kind of monodisperse magnetic this application involves monodisperse magnetic porous silica microballoon field
Silicon dioxide microsphere and preparation method thereof.
Background technique
Porous silica has good high specific surface area, high mechanical strength, stability, good biocompatibility and Yi Xiu
The features such as decorations.Magnetic nano-particle can be transported from liquid phase separation or specific aim to particular portion under the action of external magnetic field
Position, be widely used in fields such as adsorbing separation, catalysis and targeted delivery of drugs, but due to its stability difference and it is easy to reunite the disadvantages of,
Using being subject to certain restrictions.Porous silica and magnetic nano-particle are be combined with each other and prepare composite material, then can be overcome
The advantages of this disadvantage, porous silica and magnetic nano-particle, can be effectively bonded together, to have more extensively
Practical value.
Magnetic porous silicon dioxide microsphere is due to can be used for characteristics such as high-specific surface area, magnetism, low toxicity and easy modifications
The fields such as magnetic bio separation, heterogeneous catalysis, enzyme immobilization, the orientation transport of drug and the processing of water pollution.Therefore, it prepares
The porous magnetic silicon dioxide microsphere for providing controllable cellular structure, pattern and particle size has a very big significance.
The porous magnetic silicon dioxide microsphere prepared at present is mainly core-shell structure, and preparation method is main are as follows: first prepares magnetic
Property nanoparticle core, then its surface carry out sol gel, in the sol-gel process be added surfactant can make
Standby porous magnetic silica out.Wherein surfactant can also make it have very strong with the effect of the magnetic nano-particle of oiliness
Hydrophily is transferred to water phase.For example, Deng et al. (Deng, Y.H.et al.J.Am.Chem.Soc.2008,130,28-29.)
The magnetic silicon dioxide composite microsphere of the superparamagnetism of preparation, i.e., with the ferroferric oxide magnetic nano-particles of Silica-coated
For core, mesoporous silicon oxide is shell.Its specific preparation method is first to prepare Fe in the method for solvent heat3O4Magnetic nano particle
The average grain diameter of son, the magnetic nano-particle is 300nm or so, is polymerized by the magnetic particle of 15nm or so；Compound magnetic
The preparation of property microballoon is then with Fe3O4Particle is core, first in acid condition, using TEOS as silicon source, carries out sol gel,
Fe3O4Particle surface uniformly wraps up one layer of non-porous silicas, prevents magnetic particle from reuniting；It again on this basis, is soft with CTAB
Template, TEOS are silicon source, and ammonium hydroxide is alkali, carry out the sol gel of second step, that is, produce Fe3O4+nSiO2+CTAB/
SiO2Complex microsphere；CTAB is removed by solvent-extracted mode again, mesoporous silicon oxide shell can be obtained；It prepares about
The Fe of 390nm3O4+nSiO2+m/SiO2Complex microsphere, wherein nSiO2Indicate nonporous silica silicon layer, m/SiO2Indicate mesoporous two
Silica shell；The complex microsphere can be used to the Microcystin in rapidly and efficiently adsorbent solution.In addition, Gai et al. (Gai,
S.L.et al.Adv.Funct.Mater.2010,20,1166-1172.) with two similar step packet silicon process prepare porous nucleocapsid
Structure magnetic earth silicon material, and fluorescent decoration is carried out to it, so that multifunctional material is prepared, for ibuprofen pharmaceutical
Sustained release.Similar method is utilized, many researchers also prepare the porous magnetic silicon dioxide microsphere of core-shell structure, and will
It is used for bio-separation, catalysis, the absorption of mercury ion, medicament transport carrier and magnetic resonance imaging etc..Vald é s-Sol í s et al.
(Vald é s-Sol í s, T.et al.Chem.Mater.2009,21,1806-1814.) casts (Nano- using based on nanometer
Casting method) prepares porous magnetic silicon dioxide composite material.Author first prepares porous silica silicon materials, such as
Then SBA-15 deposits to molysite in the hole of silica, add ethylene glycol and enter infiltration to it；By sample after infiltration
In the lower 450 DEG C of calcinings 2h of nitrogen atmosphere, molysite is set to generate magnetic iron oxide, to prepare porous magnetic earth silicon material.
Although wherein magnetic nano-particle is distributed on entire silica substrate material the composite material of Vald é s-Sol í s preparation, and
Reunited together by part magnetic nano-particle；But the porous magnetic earth silicon material that this method is prepared is due to magnetic
The introducing of property nanoparticle, specific surface area and Kong Rong are greatly reduced compared to initial porous silica, and not
Ball-type.Chinese patent CN201310514541.1 is prepared for a kind of thiol-functionalizedmagnetic magnetic silica nano-material, by altogether
The precipitation method first prepare magnetic ferroferric oxide particle, recycle sol-gel method to carry out Silica-coated to it, prepare
Compound particle partial size between 20-30nm, be not micron order.
The magnetic silica microballoon prepared at present has the following deficiencies: (1) mostly partial size only has several hundred rans, and
And partial size and aperture are uncontrollable, wider distribution, cellular structure is uncontrollable, and generally non-interconnected hole limits it to a certain extent
Using；(2) structure is mostly core-shell structure, and magnetic nano-particle is not uniform is dispersed in the skeleton structure of silica；(3)
Magnetic particle is mostly Fe3O4, it need to be prepared in advance using coprecipitation or oil heating, it is cumbersome, and non-refractory, oxidizable, magnetic
Property easily disappears.
Summary of the invention
The purpose of the application is to provide a kind of new monodisperse magnetic porous silica microballoon and preparation method thereof.
The application uses following technical scheme:
The one side of the application discloses a kind of preparation method of the monodisperse magnetic porous silica microballoon of the application,
Including using monodispersed porous polymer microballoon as template, the in-situ preparation magnetic Fe in the duct of porous polymer microballoon3O4,
Pass through the sol gel and Fe of silicon source again3O4It is oxidized to γ-Fe2O3, it is compound micro- to form magnetic high-molecular-silica
Porous polymer microballoon is removed in ball, final high temperature calcining, i.e. acquisition monodisperse magnetic porous silica microballoon.Wherein, magnetic
Macromolecule-SiO 2 composite microsphere, which refers to, adsorbs magnetic material and silica formed in the duct of porous polymer microballoon
Complex microsphere removes polymer microsphere, that is, is left magnetic porous silica after microballoon calcining.
It should be noted that the key of the application be to prepare using monodisperse porous polymer microsphere as template it is magnetic porous
Silicon dioxide microsphere, wherein " in the hole of porous polymer microballoon in-situ preparation magnetism γ-Fe2O3, then pass through sol gel
The in-situ preparation silica in the hole of porous polymer microballoon " is described by structural order, specific in one kind of the application
It is first in-situ preparation Fe in preparation method3O4, then in-situ preparation silica, then again by Fe3O4It is oxidized to γ-Fe2O3。
It should also be noted that, the monodispersed porous polymer microballoon of the application, is that conventional can be purchased by market
The porous polymer microballoon bought can also voluntarily be prepared by polymerization reaction, for example, dispersin polymerization, seeding polymerization, emulsion polymerization,
The polymerizations such as emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization and suspension polymerisation；Also, the application uses porous
Polymer microsphere can remove that is, after high-temperature calcination there are one crucial feature.
Preferably, the preparation method of the application specifically includes following steps,
(1) monodispersed porous polymer microballoon is carried out sulfonated；Wherein, sulfonated is by porous polymer microballoon table
Face modification has sulfonic acid group；
(2) sulfonated porous polymer microballoon is mixed with source of iron, carries out ionic adsorption, source of iron includes molar ratio 2:1
Fe3+And Fe2+；Source of iron, which refers to, in the application is capable of providing Fe3+And Fe2+Salt, such as FeCl2、FeCl3；Wherein, ion is inhaled
Attached is to be adsorbed using sulfonic group to iron ion and ferrous ion；
(3) ammonium hydroxide, in-situ preparation Fe are directly added into the reaction solution of step (2)3O4；
(4) in-situ preparation Fe3O4Afterwards, the ethanol solution of silicon source is added dropwise into reaction solution, carries out sol gel, filter,
Washing obtains polymer microsphere-Fe3O4SiO 2 composite microsphere；Wherein, sol gel in the prior art, colloidal sol-
Gelation prepares that silica is similar, and only the application is that the hole of porous polymer microballoon is penetrated into using the ethanol solution of silicon source
In, fabricated in situ silica；
(5) polymer microsphere-Fe for preparing step (4)3O4SiO 2 composite microsphere is scattered in acetone, and nitre is added
Sour cerium ammonium, by magnetic Fe3O4In-situ oxidation is at γ-Fe2O3, obtain polymer microsphere-γ-Fe2O3SiO 2 composite microsphere；
(6) polymer microsphere-γ-Fe for preparing step (5)2O3After SiO 2 composite microsphere filtering, drying, it is placed in
The calcining of Muffle furnace high temperature removes polymer microsphere template, that is, obtains the monodisperse magnetic porous silica microballoon of the application.
Preferably, porous polymer microballoon is polystyrene type microballoon, polystyrene analog derivative microballoon, polyacrylate
Any one in glycidol esters microballoon or polyacrylate glycidol ester derivative microballoon.
It is furthermore preferred that porous polymer microballoon is poly (glycidyl methacrylate) microballoon, polystyrene/divinylbenzene
It is any one in microballoon, polystyrene microsphere, poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microballoon
Kind.
Preferably, the partial size of porous polymer microballoon is 200 nanometers -2000 microns, and the aperture of porous polymer microballoon is 2
- 2000 nanometers of nanometer, the degree of cross linking of porous polymer microballoon are 0~100%.
It should be noted that the preparation method of the application, can select partial size is 200 nanometers -2000 microns of porous height
Molecule microballoon is template, and the partial size of prepared monodisperse magnetic porous silica microballoon can pass through porous polymer microballoon
Template partial size and reaction condition control size.
Preferably, in step (1), to monodispersed porous polymer microballoon carry out it is sulfonated include, using the concentrated sulfuric acid or
Sodium sulfite handles porous polymer microballoon.
Preferably, silicon source is tetraalkoxysilane, more preferably ethyl orthosilicate.
Preferably, the condition of high-temperature calcination is, rises to 500-600 DEG C from room temperature with the speed of 1-10 DEG C/min, and in
500-600 DEG C of holding 2-20h.
The another side of the application discloses the monodisperse magnetic porous silica microballoon of the preparation method preparation of the application.
It should be noted that the monodisperse magnetic porous silica microballoon and existing magnetic silica of the application are micro-
Ball is compared, and first, the monodisperse magnetic porous silica microballoon of the application, due to using special preparation method, hole is
Connection, also, the size in aperture, porosity etc. are all controllable, it can according to the material selected in preparation method, control aperture
Size and porosity etc.；Second, the monodisperse magnetic porous silica microballoon of the application, magnetic material is property γ-
Fe2O3, magnetism ratio Fe3O4It is more stable, and high temperature resistant；Third, it is magnetic in the monodisperse magnetic porous silica microballoon of the application
Nanoparticle is dispersed in the ball-type skeleton of silica, and unconventional core-shell structure；4th, the list of the application
Dispersed magnetic porous silica microballoon, particle size is controllable, prepares material according to used, prepared by a kind of of the application
In method, specifically, it is more that prepared magnetism can be controlled according to the particle size of selected porous polymer microsphere template
The particle size of hole microballoon.The dispersed magnetic porous silica microballoon of the application have uniform particle diameter, partial size and aperture it is controllable,
Hole connection introduces that magnetic nano particle submethod is simple and the characteristics such as magnetic stability.
Preferably, the partial size of monodisperse magnetic porous silica microballoon is 200 nanometers -2000 microns.
It should be noted that the partial size of the monodisperse magnetic porous silica microballoon of the application is 200 nanometer -2000 micro-
Rice, which refers to, can prepare the porous dioxy of monodisperse magnetic that partial size is 200 nanometers -2000 microns by preparing the selection of material
SiClx microballoon.
The beneficial effects of the present application are as follows:
The preparation method of the application has the advantages that partial size and aperture are controllable using porous polymer microballoon as template, in situ
Synthesize Fe3O4And it is oxidized to γ-Fe2O3, the method for introducing magnetic nano-particle is simple to operation, is monodisperse magnetic porous two
Silicon oxide microsphere provides a kind of simple, easy to operate, and efficient preparation method.The monodisperse magnetic porous two of the application preparation
Silicon oxide microsphere has partial size and aperture controllable, is in hole connectivity structure, and magnetic stability, high temperature resistant.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of monodisperse magnetic porous silica microballoon in the embodiment of the present application；
Fig. 2 is the graph of pore diameter distribution of monodisperse magnetic porous silica microballoon in the embodiment of the present application；
Fig. 3 is the B-H loop of monodisperse magnetic porous silica microballoon in the embodiment of the present application.
Specific embodiment
The application has studied a kind of preparation method of new monodisperse magnetic porous silica microballoon, and is based on the party
Method has developed a kind of new monodisperse magnetic porous silica microballoon.Preparation method based on the application, single point of the application
Sperromagnetism porous silica microballoon, partial size and aperture are all controllable, also, are connection between hole.It is appreciated that the application
Preparation method be finally to get rid of the porous polymer microsphere template using porous polymer microballoon as template, therefore, institute
The porous silica microballoon of preparation, what hole was necessarily connected to.Also, the partial size of prepared porous silica microballoon and
Aperture can be controlled by porous polymer microsphere template.
In the application, " PGMA/EGDMA " is poly (glycidyl methacrylate)/ethylene glycol dimethacrylate
Abbreviation, " PS/DVB " is the abbreviation of polystyrene/divinylbenzene.
The application is described in further detail below by specific embodiment.Following embodiment only to the application carry out into
One step explanation, should not be construed as the limitation to the application.
Embodiment one
This example prepares single point of this example using 4.54 μm of partial size commercially available of monodisperse porous PGMA/EGDMA microballoon as template
Sperromagnetism porous silica microballoon, it is specific the preparation method is as follows:
(1) 4.54 μm of 20g partial size monodisperse porous PGMA/EGDMA microballoon ultrasonic disperses are weighed in 500mL water, are added
20g sodium sulfite, 160rpm mechanical stirring, reaction for 24 hours, carry out sulfonated；It filters, is washed respectively with water and ethyl alcohol after reaction
It washs 3 times, it is spare in 50 DEG C of oven dryings.
(2) Fe is configured2+: Fe3+Molar ratio is the source of iron solution of 1:2: weighing 1.645g FeCl2·4H2O and 4.34g
FeCl3·6H2O is dissolved in 20mL water, that is, is made into source of iron solution, after source of iron solution vacuumizes, N2Under save backup.By 0.5g
The source of iron solution that 0.125mL has been prepared is added in 20mL water in the sulfonated PGMA/EGDMA microballoon ultrasonic disperse of step (1),
Adsorb 12h.
(3) after adsorbing 12h, 1mL 28wt% ammonium hydroxide is added directly into solution, mechanical stirring 3h produces porous magnetic
Property Fe3O4/ high molecular composite microsphere.
(4) continue to add 2mL 28wt% ammonium hydroxide in the reaction solution of step (3), 10mL water and 80mL ethyl alcohol be added,
2g TEOS is dissolved into 10mL ethyl alcohol by ultrasonic disperse microballoon, and the ethanol solution of TEOS is slowly dropped to reaction flask with peristaltic pump
In, it is reacted at room temperature for 24 hours after being added dropwise.It filters after reaction, is washed respectively 3 times with water and ethyl alcohol, high score can be prepared
Sub- microballoon-Fe3O4SiO 2 composite microsphere.
(5) it weighs 0.045g ammonium ceric nitrate to be dissolved in 4mL acetone, polymer microsphere-Fe prepared by step (4)3O4- two
Silica complex microsphere is scattered in acetone, then ceric ammonium nitrate solution is added thereto, ultrasonic 3h, turns magnetic ferroferric oxide
Become magnetic γ-Fe2O3, then this complex microsphere filtered, it washs, it is dry, obtain polymer microsphere-γ-Fe2O3Silica
Complex microsphere, i.e. magnetic high-molecular-SiO 2 composite microsphere.
(6) by the polymer microsphere-γ-Fe of step 52O3SiO 2 composite microsphere is placed in Muffle furnace, with 2 DEG C/
The speed of min rises to 600 DEG C, high-temperature calcination 6h, removes PGMA/EGDMA microballoon chelating polymer template to get the monodisperse of this example is arrived
Magnetic porous silicon dioxide microsphere.
Monodisperse magnetic porous silica microballoon prepared by this example is observed using scanning electron microscope, as a result such as Fig. 1
Shown, A figure is the view under smaller amplification factor in figure, and B figure is the view under higher magnification；As it can be seen that this example is prepared
Monodispersity of uniform size good magnetic porous silicon dioxide microsphere.
Further this example surveys the monodisperse magnetic porous silica microballoon prepared using specific surface area analysis instrument
N2The attached isothermal curve of absorption-desorption, obtains its graph of pore diameter distribution, as a result as shown in Figure 2, it is seen that the magnetic porous titanium dioxide of this example
The aperture of silicon microballoon is mainly distributed on 13nm or so, and the macropore containing 50-100nm or so.
The B-H loop for the magnetic porous silicon dioxide microsphere that this example is prepared passes through vibrating specimen magnetometer at room temperature
It measures, as a result such as Fig. 3, it can be seen that its saturation magnetization is 1.25emu/g, it was demonstrated that its magnetic properties.
Embodiment two
This example using 7.42 μm of partial size commercially available of monodisperse porous PGMA/EGDMA microballoon as template, alternative embodiment one
4.54 μm of monodisperse porous PGMA/EGDMA microballoons, prepare monodisperse magnetic porous silica microballoon.The preparation method of this example
Compared with embodiment one, the difference is that the additional amount of source of iron solution is 0.5mL in step (2)；By 3g TEOS in step (4)
It is dissolved into the ethanol solution that TEOS is made into 10mL ethyl alcohol；In step (5), 0.06g ammonium ceric nitrate is dissolved in 4mL acetone and is made into
Ceric ammonium nitrate solution；Remaining step and parameter are all the same as example 1.
Monodisperse magnetic porous silica microballoon prepared by this example is observed using scanning electron microscope, the results show that
This example has prepared the good magnetic porous silicon dioxide microsphere of monodispersity of uniform size, also, magnetic porous silica
Microballoon micropore is evenly distributed.Pore-size distribution system is carried out using porous silica microballoon of the identical method of embodiment one to this example
Meter analysis, the results show that the porous silica microballoon pore size of this example is uniform, is largely distributed in 20nm or so.Also,
The porous silica microballoon of this example, saturation magnetization are suitable with the magnetic porous silicon dioxide microsphere of embodiment one.
Embodiment three
This example prepares the monodisperse magnetic of this example using 6.24 μm of partial size commercially available of monodisperse porous PS/DVB microballoon as template
Property porous silica microballoon, it is specific the preparation method is as follows:
(1) 6.24 μm of 5g partial size monodisperse porous PS/DVB microballoons are weighed, are placed in three-neck flask, the dense sulphur of 50mL is added
Acid stirs evenly, 160rpm mechanical stirring, and reaction for 24 hours, carries out sulfonated；It filters, is washed respectively with water and ethyl alcohol after reaction
It washs 3 times, it is spare in 50 DEG C of oven dryings.
(2) Fe is configured2+: Fe3+Molar ratio is the source of iron solution of 1:2: weighing 1.645g FeCl2·4H2O and 4.34g
FeCl3·6H2O is dissolved in 20mL water, that is, is made into source of iron solution, after source of iron solution vacuumizes, N2Under save backup.By 0.5g
The source of iron solution that 0.125mL has been prepared is added in 20mL water in the sulfonated PS/DVB microballoon ultrasonic disperse of step (1), absorption
12h。
(3) after adsorbing 12h, 1mL 28wt% ammonium hydroxide is added directly into solution, mechanical stirring 3h produces porous magnetic
Property Fe3O4/ high molecular composite microsphere.
(4) continue to add 2mL28wt% ammonium hydroxide in the reaction solution of step (3), 10mL water and 80mL ethyl alcohol is added, surpass
2g TEOS is dissolved into 10mL ethyl alcohol by sound dispersion microsphere, and the ethanol solution of TEOS is slowly dropped to reaction flask with peristaltic pump
In, it is reacted at room temperature for 24 hours after being added dropwise.It filters after reaction, is washed respectively 3 times with water and ethyl alcohol, high score can be prepared
Sub- microballoon-Fe3O4SiO 2 composite microsphere.
(5) it weighs 0.045g ammonium ceric nitrate to be dissolved in 4mL acetone, polymer microsphere-Fe prepared by step (4)3O4- two
Silica complex microsphere is scattered in acetone, then ceric ammonium nitrate solution is added thereto, ultrasonic 3h, turns magnetic ferroferric oxide
Become magnetic γ-Fe2O3, then this complex microsphere filtered, it washs, it is dry, obtain polymer microsphere-γ-Fe2O3Silica
Complex microsphere.
(6) by the polymer microsphere-γ-Fe of step 52O3SiO 2 composite microsphere is placed in Muffle furnace, with 2 DEG C/
The speed of min rises to 550 DEG C, high-temperature calcination 6h, removes PS/DVB microballoon chelating polymer template to get the monodisperse magnetic of this example is arrived
Porous silica microballoon.
Monodisperse magnetic porous silica microballoon prepared by this example is observed using scanning electron microscope, the results show that
This example has prepared the good magnetic porous silicon dioxide microsphere of monodispersity of uniform size.Using the identical method of embodiment one
Pore-size distribution statistical analysis is carried out to the porous silica microballoon of this example, the results show that the porous silica microballoon of this example
Aperture is mainly in 18nm or so.Also, the porous silica microballoon of this example, the magnetism of saturation magnetization and embodiment one
Porous silica microballoon is suitable.
Example IV
This example is using the monodisperse porous PS/DVB microballoon of commercially available partial size 10.36 as template, the partial size of alternative embodiment three
6.24 μm of monodisperse porous PS/DVB microballoon prepares the monodisperse magnetic porous silica microballoon of this example.Remaining step and
Parameter is identical as embodiment three.
Likewise, being observed using scanning electron microscope monodisperse magnetic porous silica microballoon prepared by this example, tie
Fruit shows that this example has prepared the good magnetic porous silicon dioxide microsphere of monodispersity of uniform size.Using one phase of embodiment
Same method carries out pore-size distribution statistical analysis to the porous silica microballoon of this example, the results show that the porous dioxy of this example
SiClx microballoon aperture is mainly distributed on 25nm or so.Also, the porous silica microballoon of this example, saturation magnetization and reality
The magnetic porous silicon dioxide microsphere for applying example one is suitable.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, and it cannot be said that this Shen
Specific implementation please is only limited to these instructions.For those of ordinary skill in the art to which this application belongs, it is not taking off
Under the premise of from the application design, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the protection of the application
Range.
Claims (10)
1. a kind of preparation method of monodisperse magnetic porous silica microballoon, it is characterised in that: including with monodisperse porous height
Molecule microballoon is template, the in-situ preparation magnetic Fe in the duct of porous polymer microballoon3O4, then the sol-gel for passing through silicon source
Change and Fe3O4Oxidation generates γ-Fe2O3, magnetic high-molecular-SiO 2 composite microsphere is formed, institute is removed in final high temperature calcining
Porous polymer microballoon is stated, that is, obtains the monodisperse magnetic porous silica microballoon；
The preparation method specifically includes following steps,
(1) monodispersed porous polymer microballoon is carried out sulfonated；
(2) sulfonated porous polymer microballoon is mixed with source of iron, carries out ionic adsorption, the source of iron includes molar ratio 2:1
Fe3+And Fe2+；
(3) ammonium hydroxide, in-situ preparation Fe are directly added into the reaction solution of step (2)3O4；
(4) in-situ preparation Fe3O4Afterwards, the ethanol solution of silicon source is added dropwise into reaction solution, carries out sol gel, is filtered, washed
Obtain polymer microsphere-Fe3O4SiO 2 composite microsphere；
(5) polymer microsphere-Fe for preparing step (4)3O4SiO 2 composite microsphere is scattered in acetone, and cerous nitrate is added
Ammonium, by magnetic Fe3O4In-situ oxidation is at γ-Fe2O3, obtain polymer microsphere-γ-Fe2O3SiO 2 composite microsphere；
(6) polymer microsphere-γ-Fe for preparing step (5)2O3After SiO 2 composite microsphere filtering, drying, it is placed in Muffle
The calcining of furnace high temperature, removes polymer microsphere template, that is, obtains the monodisperse magnetic porous silica microballoon.
2. preparation method according to claim 1, it is characterised in that: the porous polymer microballoon is that polystyrene type is micro-
Ball, polystyrene analog derivative microballoon, polyacrylate glycidol esters microballoon or polyacrylate glycidol esters are spread out
Any one in biological microsphere.
3. preparation method according to claim 2, it is characterised in that: the porous polymer microballoon is polymethylacrylic acid
Glycidol ester microsphere, polystyrene/divinylbenzene microspheres, polystyrene microsphere, poly (glycidyl methacrylate)/second two
Any one in alcohol dimethylacrylate microballoon.
4. preparation method according to claim 1, it is characterised in that: the partial size of the porous polymer microballoon is received for 200
- 2000 microns of rice, the aperture of porous polymer microballoon are 2 nanometers -2000 nanometers, the degree of cross linking of porous polymer microballoon is 0~
100%.
5. preparation method according to claim 1, it is characterised in that: in the step (1), to monodispersed porous high score
Sub- microballoon carries out sulfonated including handling porous polymer microballoon using the concentrated sulfuric acid or sodium sulfite.
6. preparation method according to claim 1, it is characterised in that: the silicon source is tetraalkoxysilane.
7. preparation method according to claim 1, it is characterised in that: the silicon source is ethyl orthosilicate.
8. preparation method according to claim 1-7, it is characterised in that: the condition of the high-temperature calcination is, with
The speed of 1-10 DEG C/min rises to 500-600 DEG C from room temperature, and in 500-600 DEG C of holding 2-20h.
9. the monodisperse magnetic porous silica microballoon of preparation method preparation according to claim 1-8.
10. monodisperse magnetic porous silica microballoon according to claim 9, it is characterised in that: the monodisperse magnetic
Property porous silica microballoon partial size be 200 nanometers -2000 microns.
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| CN108609649B (en) * | 2018-05-22 | 2020-06-09 | 河北工业大学 | Preparation method of sea urchin-shaped magnetic hollow microspheres |
| CN108911599B (en) * | 2018-07-18 | 2020-10-09 | 浙江工业大学 | Method for simultaneously preparing iron oxide and silicon dioxide aerogel pad from iron tailings |
| CN110767437B (en) * | 2018-07-26 | 2021-06-25 | 香港城市大学深圳研究院 | Preparation method of magnetic nanoparticles with silicon dioxide-coated ferroferric oxide core-shell structure |
| CN109485052A (en) * | 2018-09-20 | 2019-03-19 | 四川大学 | A kind of preparation method of macropore superparamagnetism array type earth silicon material |
| CN109865496A (en) * | 2019-02-26 | 2019-06-11 | 北京大学深圳研究生院 | Magnetic silica filler, magnetic affine filler and preparation method and purposes |
| CN111498911B (en) * | 2020-04-22 | 2021-11-05 | 常熟理工学院 | Purple Fe with monodisperse hollow structure3O4@SiO2Material and preparation method |
| CN111599588B (en) * | 2020-06-08 | 2022-04-05 | 杭州昆腾纳米科技有限公司 | Center-radial filling type composite superparamagnetic microsphere and preparation method and application thereof |
| CN112429910B (en) * | 2020-10-30 | 2022-12-06 | 华北水利水电大学 | Water resource treatment and filtration method and device for water conservancy construction |
| DE102020132495B3 (en) | 2020-12-07 | 2022-05-12 | Bundesrepublik Deutschland, Wirtschaft und Energie, Bundesanstalt für Materialforschung und -prüfung (BAM) | Particles composed of an organic polymer core, a first inorganic oxide shell containing a magnetic material, and a mesoporous second inorganic shell |
| CN112724305B (en) * | 2020-12-15 | 2023-05-12 | 中国科学院苏州生物医学工程技术研究所 | Monodisperse quantum dot encoded magnetic microsphere |
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