CN101205420B - Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof - Google Patents
Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof Download PDFInfo
- Publication number
- CN101205420B CN101205420B CN2007101718279A CN200710171827A CN101205420B CN 101205420 B CN101205420 B CN 101205420B CN 2007101718279 A CN2007101718279 A CN 2007101718279A CN 200710171827 A CN200710171827 A CN 200710171827A CN 101205420 B CN101205420 B CN 101205420B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- particle
- inorganic
- active agent
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention belongs to the nano-composite material technology field, in particular to a magnetic inorganic nano-particle/ordered mesoporous silica core-shell microsphere and a preparation method thereof. The invention first utilizes sol-gel chemical synthesis method, coats a layer of amorphous silica on the surface of a plurality of magnetic inorganic nano-particles, then utilizes self-assembly of an organic surfactant as structure-directing agent and inorganic species in the solution, coats a layer of ordered meso-structured silica/surfactant composite material on the surface of the magnetic inorganic nano-particle/ silica composite microsphere, removes the surfactant through solvent extraction, and obtains the ordered mesoporous magnetic inorganic nano-particle/silica core-shell structure composite microsphere material. The composite microsphere has high specific surface area, strong magnetic responsiveness, and wide application prospect in bioseparation and bioabsorption. The invention is simple in method, easy in obtaining raw materials, and suitable for large scale production.
Description
Technical field
The invention belongs to advanced nano composite material and technical field, be specifically related to a kind of magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon and preparation method thereof.
Technical background
In recent years, the needs of Along with people's aspect bioanalysis separation, enzyme curing, medical diagnosis on disease have magnetic iron oxide particle as nuclear, and earth silicon material receives people's extensive concern as the nucleocapsid complex microsphere of shell.Its reason is that this complex microsphere has the magnetic response characteristic, can simplify to make things convenient for compartment analysis, and is very low for the toxicity of organism, and can be through the group of chemically modified in silica sphere grafting different functionsization, thereby increases its Application Areas.
Than traditional earth silicon material, the characteristic of the mesopore orbit of the high-ratio surface that the ordered mesoporous silica dioxide material has, high pore volume, homogeneous is with a wide range of applications at aspects such as catalysis, fractionation by adsorption.To sum up visible, the complex microsphere with magnetic response performance, order mesoporous structure can make full use of the advantage of above-mentioned two types of materials, has more wide application prospect in the compartment analysis field.But up to the present, being nuclear with the magnetic oxide particle, is that the synthesizing of nucleocapsid composite nano-microsphere of shell also rarely has report with the ordered mesoporous material.In the existing report, institute's synthetic matrix material have magnetic response weak effect, matrix material shape inhomogeneous, deficiency such as can't finely in water, disperse.In addition, it is unordered or be parallel to the mesoporous of microsphere surface that institute's synthetic material is had, aspect mass transfer, has certain deficiency.(Kim，J.；Lee，J.E.；Lee，J.；Yu，J.H.；Kim，B.C.；An，K.；Hwang，Y.；Shin，C.H.；Park，J.G..；Kim，J.；Hyeon，T.；J.Am.Chem.Soc.，2006，128，688-689.Lin，Y.S.；Wu，S.H.；Hung，Y.；Chou，Y.H.；Chang，C.；LIn，M.L.；Tsai，C.P.；Mou，C.Y.；Chem.Mater.，2006，18，5170-5172.Giri，S.；Trewyn，B.G.；Stellmaker，M.P.；Lin，V.S.Y.；Angew.Chem.Int.Ed.，2005，44，5038-5044.Zhao，W.R.；Gu，J.L.；Zhang，L.X.；Chen，H.R.；Shi，J.L.；J.Am.Chem.Soc.，2005，127，8916-8917.)
Different and various magnetic particles/meso-porous titanium dioxide silicon composite particles of being reported before, the magnetic inorganic nano-particle with ordered mesoporous pore canals/silicon dixoide nucleocapsid structure complex microsphere that the present invention reported have the corresponding height of magnetic, microballoon shape homogeneous, mesoporous in order and be easy to the characteristic of mass transfer diffusion.In the compound method that the present invention reported, make full use of the characteristic of magneticsubstance, adopted magnet to separate, had the characteristic that raw material is easy to get, method is simple rapidly, synthetic materials purity is high, be suitable for scale operation.Because high-ratio surface, high pore volume, the mesoporous characteristic of uniform and ordered that it had have important application prospects in the fractionation by adsorption field.
Summary of the invention
The object of the present invention is to provide that a kind of magnetic response is effective, the shape homogeneous, have magnetic inorganic nano-particle/silica core-shell microspheres of ordered mesoporous pore canals and preparation method thereof.
A kind of magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon proposed by the invention; Make by following method: with the magnetic inorganic nanoparticle as seed grain; Utilize the principle of sol-gel chemistry; Adopt silicon source presoma hydrolysis; At first coat the last layer soft silica, utilize in sol-gel chemistry and the solution self-assembly behavior then, have the tensio-active agent and the silicon dioxide composite material of orderly mesoscopic structure at soft silica laminar surface coating one deck as tensio-active agent and the inorganic silicon species of structure directing agent on magnetic particle surface; Remove organic surface active agent through SX at last, promptly obtain having the inorganic nano-particle/silica core-shell complex microsphere of magnetic and ordered mesoporous pore canals.The size of institute's synthetic complex microsphere is 200nm～1 μ m; Specifically through regulating size, the amorphous silica thickness of coating and the thickness control of organic surface active agent and silicon dioxide composite material of magnetic inorganic nanoparticle; Cross the thickness of organic surface active agent/inorganic silicon dioxide matrix material of controlling initial magnetic microsphere size, the silicon-dioxide layer thickness that coats and coating and realize that the specific surface area of microballoon is 100m
2/ g～600m
2/ g, pore volume are 0.1cm
3/ g～0.8cm
3Between/the g, the mesoporous aperture size that microballoon had is 2nm～10nm.
In the microballoon, inorganic nano-particle is of a size of 100nm～800nm, and the amorphous silica layer thickness is 10nm～820nm, and the thickness of organic surface active agent/inorganic silicon dioxide matrix material is 20nm～880nm.The size of microballoon is 200nm～1 μ m.
Among the present invention, described inorganic nano-particle disperses in polar solvent easily, has magnetic.Particulate is of a size of 100nm～800nm, and the material of this particulate can be Z 250 (Fe
3O
4), γ-red oxide of iron (γ-Fe
2O
3), NiFe
2O
4, CuFe
2O
4, wherein one or more of nano iron particles, nanometer nickel, nanometer cobalt.
Among the present invention, employed silicon source is one or more in water glass, tetraethoxysilance (TEOS), the methyl silicate (TMOS).
Among the present invention, the silicon source employed catalyzer of presoma hydrolysis is an acidic catalyst or basic catalyst.Basic catalyst is sodium hydroxide (NaOH), Pottasium Hydroxide (KOH) or strong aqua (NH
3H
2O).Acid an acidic catalyst is one or more in acetic acid, acetate, the Hydrogen chloride (HCl).
Among the present invention, employed tensio-active agent is non-ionics or ionogenic surfactant.Non-ionics is the small molecules C that contains polyethers
nH
2n+1EO
mIn one or more (n=5-12, m=10-20).Ionogenic surfactant is alkyl quaternaries tensio-active agent C
nAmong the TAB one or more (n=12-18).
Among the present invention, employed solvent is the mixing solutions of alkyl alcohol and water, and alkyl alcohol wherein is one or more types of methyl alcohol, ethanol, Virahol.The mass ratio of alkyl alcohol and water is 9: 1～1: 9.
Among the present invention; Coat in the colloidal sol-gel chemistry synthetic system of amorphous silica on the inorganic nanoparticles surface; Inorganic magnetic nanoparticle mass percent is 0.50wt%～5wt%; Silicon source quality per-cent is 0.1wt%～0.5wt%, and catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent.Continue to coat in the synthetic system of organic surfactivity and silicon dioxide composite material on the surface of amorphous silica; Surface deposition the mass percent of inorganic nanoparticles of silicon-dioxide be in 0.50wt%～5wt% colloidal sol-gel chemistry synthetic system; Inorganic magnetic nanoparticle mass percent is 0.5wt%～5wt%; The tensio-active agent mass percent is 0.5wt～2wt%; Silicon source quality per-cent is 0.2wt%～0.5wt%, and catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent.
Among the present invention, the order mesoporous structure of silicon-dioxide comprises various meso-hole structures with tubulose duct, spherical duct in the prepared composite micro-sphere material.Its pore passage structure can be p6mm on spacer,
P6
3/ mmc,
One or several mixed structure wherein.
Embodiment
Embodiment 1:
(1) size is dispersed in 80ml ethanol at the 0.1g of about 300nm magnetic ferroferric oxide particulate; In 20ml deionized water and the 1ml strong aqua (28wt%); Add 0.3g tetraethoxysilance (TEOS), stir 6h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition; Product is separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature for use.
(2) with the magnetic ferroferric oxide complex microsphere ultra-sonic dispersion after the surface deposition layer of silicon dioxide in containing 60ml ethanol; The 80ml deionized water; 1.00g in the mixing solutions of strong aqua and 0.30g cetyl trimethyl ammonia bromide (CTAB), stirring 0.5h dropwise adds 0.40g tetraethoxysilance (TEOS) after making solution evenly; Drip complete continued and stir 6h; Obtain magnetic ferroferric oxide/the contain SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 48h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 40.8emu/g, and particle diameter is 410nm, and mesoporous aperture is 2.1nm.
Embodiment 2:
(1) size is dispersed in 100ml ethanol at the 0.1g of about 500nm magnetic ferroferric oxide particulate; In 10ml deionized water and the 1ml strong aqua (28wt%); Add 0.25g tetraethoxysilance (TEOS), stir 7h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition; Product is separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature for use.
(2) with the magnetic ferroferric oxide complex microsphere ultra-sonic dispersion after the surface deposition layer of silicon dioxide in containing 90ml ethanol; The 60ml deionized water; 1.00g in the mixing solutions of strong aqua and 0.30g cetyl trimethyl ammonia bromide (CTAB), stirring 0.8h dropwise adds 0.40g tetraethoxysilance (TEOS) after making solution evenly; Drip complete continued and stir 5h; Obtain magnetic ferroferric oxide/the contain SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 48h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 38.0emu/g, and particle diameter is 620nm, and mesoporous aperture is 2.4nm.
Embodiment 3:
(1) with size at the 0.1g of about 300nm magnetic NiFe
2O
4Particulate is dispersed in 90ml ethanol; In 10ml deionized water and the 1ml strong aqua (28wt%); Add 0.5g tetraethoxysilance (TEOS), stir 10h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition; Product is separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature for use.
(2) with the magnetic NiFe after the surface deposition layer of silicon dioxide
2O
4The complex microsphere ultra-sonic dispersion is in containing 30ml ethanol, 110ml deionized water, 1.00g aqueous hydrochloric acid (1.0M) and 0.30g Brij 56 (C
16H
33EO
10) mixing solutions in, after stirring 0.4h and making solution evenly, dropwise add 0.40g tetramethoxysilance (TEOS), drip complete continued and stir 8h, obtain magnetic NiFe
2O
4/ containing the SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 36h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 52.7emu/g, and particle diameter is 440nm, and mesoporous aperture is 2.0nm.
Embodiment 4:
(1) size is dispersed in 80ml ethanol at the 0.1g of about 700nm magnetic γ-red oxide of iron particulate; In 20ml deionized water and the 1ml strong aqua (28wt%); Add 0.03g tetraethoxy (TEOS), stir 6h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition; Product is separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature for use.
(2) with the magnetic γ-red oxide of iron complex microsphere ultra-sonic dispersion of surface deposition layer of silicon dioxide in containing the 60ml Virahol; The 80ml deionized water; 1.00g in the mixing solutions of strong aqua and 0.30g cetyl trimethyl ammonia bromide (CTAB), stirring 1.5h dropwise adds 0.40g tetraethoxysilance (TEOS) after making solution evenly; Drip complete continued and stir 8h; Obtain magnetic γ-red oxide of iron particulate/contain SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 48h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 60.8emu/g, and particle diameter is 900nm, and mesoporous aperture is 2.2nm.
Claims (2)
1. the preparation method of a magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon; It is characterized in that concrete steps are following: with the magnetic inorganic nanoparticle as the initial seed grain; Utilize the sol-gel principles of chemistry; Adopt silicon source presoma hydrolysis, at first coat the last layer soft silica on the inorganic nano-particle surface; Utilize in the sol-gel principles of chemistry and the solution self-assembly behavior then, coat organic surface active agent and the inorganic silicon dioxide matrix material that one deck has orderly mesoscopic structure on the amorphous silica surface as the tensio-active agent and the inorganic silicon species of structure directing agent; Obtain through organic solvent extraction at last and remove organic surface active agent, promptly obtain order mesoporous and inorganic nano-particle/silica core-shell microspheres magnetic, institute's synthetic complex microsphere size is 200nm～1 μ m, and specific surface is 100m
2/ g～600m
2/ g, pore volume are 0.1cm
3/ g～0.8cm
3/ g, mesoporous aperture size is 2nm～10nm; Wherein:
Described magnetic inorganic nanoparticle is of a size of 100nm～800nm, and this microparticle material is Z 250, γ-red oxide of iron, NiFe
2O
4, CuFe
2O
4, wherein a kind of of nano iron particles, nanometer nickel or nanometer cobalt;
Employed silicon source is one or more in water glass, tetraethoxysilance, the methyl silicate;
The employed catalyzer of presoma hydrolysis is an acidic catalyst or basic catalyst in the synthesizing mesoporous silicon dioxide materials process; Basic catalyst be sodium hydroxide, Pottasium Hydroxide or strong aqua one or more, an acidic catalyst be in acetic acid or the Hydrogen chloride one or more;
Employed tensio-active agent is non-ionics or ionogenic surfactant, and wherein non-ionics is the small molecules C that contains polyethers
nH
2n+1EO
mIn one or more, n=5-12, m=10-20; Ionogenic surfactant is alkyl quaternaries tensio-active agent C
nAmong the TAB one or more, n=12-18;
Employed solvent is the mixing solutions of alkyl alcohol and water, and alkyl alcohol wherein is one or more of methyl alcohol, ethanol or Virahol, and the mass ratio of alkyl alcohol and water is 9: 1～1: 9;
Coat in the sol-gel chemosynthesis system of amorphous silica on the inorganic nanoparticles surface; Inorganic magnetic nanoparticle mass percent is 0.50wt%～5wt%; Silicon source quality per-cent is 0.1wt%～0.5wt%; Catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent; Continue to coat in the synthetic system of organic surfactivity and silicon dioxide composite material on the surface of amorphous silica; Surface deposition the mass percent of inorganic nanoparticles of silicon-dioxide be 0.5wt%～5wt%; The tensio-active agent mass percent is 0.5wt～2wt%; Silicon source quality per-cent is 0.2wt%～0.5wt%, and catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent.
2. preparation method according to claim 1 is characterized in that the order mesoporous structure of mesoporous silicon oxide in the said microballoon comprises the meso-hole structure in tubulose duct, spherical duct, is p6mm on the spacer of its pore passage structure,
P6
3/ mmc,
In one or several mixed structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101718279A CN101205420B (en) | 2007-12-06 | 2007-12-06 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101718279A CN101205420B (en) | 2007-12-06 | 2007-12-06 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101205420A CN101205420A (en) | 2008-06-25 |
| CN101205420B true CN101205420B (en) | 2012-01-18 |
Family
ID=39565909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101718279A Expired - Fee Related CN101205420B (en) | 2007-12-06 | 2007-12-06 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101205420B (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618851B (en) * | 2009-07-31 | 2012-05-09 | 华南理工大学 | Hexagonal mesoporous and nanowire complex and preparation method thereof |
| CN102059100B (en) * | 2010-12-10 | 2012-07-04 | 四川农业大学 | Method for preparing magnetic saccharomyces cerevisiae and technique for processing printing and dying wastewater by using same |
| CN102500296B (en) * | 2011-11-04 | 2013-10-30 | 同济大学 | Preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers |
| CN102628188A (en) * | 2012-04-18 | 2012-08-08 | 上海应用技术学院 | Assembling method for magnetic field oriented morphological anisotropic axiolitic mesocellular silica photonic crystal ordered film |
| CN102766357A (en) * | 2012-08-10 | 2012-11-07 | 杭州弗沃德精细化工有限公司 | Method for preparing magnetic permeability pearlescent pigment |
| CN102885784B (en) * | 2012-09-26 | 2014-03-19 | 复旦大学附属金山医院 | Method for preparing microspheres by using oil-in-nanoparticle mixed suspension-nanometer medicament-in-oil |
| CN102885782B (en) * | 2012-09-26 | 2014-03-19 | 复旦大学附属金山医院 | Growth hormone-containing nanometer medicament microspheres and preparation method thereof |
| CN102989398A (en) * | 2012-12-02 | 2013-03-27 | 复旦大学 | Magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres and preparation method thereof |
| CN103007845B (en) * | 2012-12-14 | 2014-11-19 | 无锡百运纳米科技有限公司 | Synthetic method for magnetic Fe and SiO2 microsphere |
| CN103143305A (en) * | 2013-03-27 | 2013-06-12 | 哈尔滨工业大学 | Method for synthesizing magnetic mesoporous silica nanoparticle microsphere with core-shell structure in acidic conditions |
| CN103310935A (en) * | 2013-06-05 | 2013-09-18 | 中国科学院上海硅酸盐研究所 | Silicon dioxide nano magnetic microsphere and preparation method thereof |
| CN103316614B (en) * | 2013-06-05 | 2015-08-12 | 浙江大学 | A kind of γ-Fe 2o 3/ SiO 2the preparation method of nano composite material and nanocomposite particles |
| CN103500622B (en) * | 2013-08-30 | 2017-05-10 | 复旦大学 | Magnetism inorganic nanoparticle/ordered mesopore silica nuclear shell composite microsphere and preparing method thereof |
| CN104275153B (en) * | 2014-08-22 | 2017-06-16 | 中国科学院高能物理研究所 | Imidazoles functional magnetic mesoporous silicon and its preparation method and application |
| CN104437566B (en) * | 2014-12-04 | 2016-09-07 | 江南大学 | A kind of Fe of core shell structure3o4@SiO2nanometer particle load type Cu catalyst and its preparation method and application |
| CN104826598A (en) * | 2015-04-14 | 2015-08-12 | 中山大学 | Preparation and applications of novel separation medium magnetic perhydroxycucurbit[8]uril |
| CN105903032A (en) * | 2016-05-31 | 2016-08-31 | 武汉理工大学 | Super-paramagnetic targeting dual-drug sustained-release carrier material and preparation method thereof |
| CN107930599B (en) * | 2017-08-23 | 2021-03-16 | 公安部物证鉴定中心 | Magnetic material for pretreatment of aqueous solution drug test material and preparation method thereof |
| CN108187738B (en) * | 2017-12-29 | 2020-11-20 | 中触媒新材料股份有限公司 | Preparation method and application of magnetic TS-1 molecular sieve microspherical catalyst |
| CN108405879A (en) * | 2018-04-02 | 2018-08-17 | 华东理工大学 | A kind of preparation method of nano zero valence iron@meso pore silicon oxide materials |
| CN108711480B (en) * | 2018-04-03 | 2020-07-03 | 复旦大学 | Magnetic mesoporous silica nanochain with core-shell structure and preparation method thereof |
| US10661250B2 (en) * | 2018-04-13 | 2020-05-26 | Agilent Technologies, Inc. | Synthetic silica as packing material in supported liquid extraction |
| CN109012624A (en) * | 2018-07-14 | 2018-12-18 | 桂林理工大学 | A kind of preparation method and applications of polypyrrole/magnetic mesoporous silicon |
| CN109524192B (en) * | 2018-12-27 | 2020-05-22 | 华南理工大学 | Preparation method of high-coercivity magnetic nanoparticle suspension |
| CN109646677B (en) * | 2019-02-13 | 2021-09-07 | 复旦大学附属眼耳鼻喉科医院 | Magnetic nano particle and method for preparing ocular hypertension animal model by using same |
| CN110075770B (en) * | 2019-05-11 | 2021-09-17 | 复旦大学 | Magnetic ordered mesoporous carbon-based or polymer-based core-shell structure microsphere and preparation method thereof |
| CN113019372B (en) * | 2021-03-12 | 2023-03-10 | 中国科学技术大学 | Surface silicon modified cobalt-nickel composite oxide catalyst, preparation method thereof and method for preparing methanol by catalyzing coal bed gas oxidation |
| CN114057232A (en) * | 2021-10-28 | 2022-02-18 | 复旦大学 | One-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and preparation method thereof |
| CN114392727A (en) * | 2021-12-24 | 2022-04-26 | 复旦大学 | Magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material and preparation method thereof |
| CN115177792A (en) * | 2022-08-23 | 2022-10-14 | 山东大学 | Preparation method of photo-crosslinking '4D' IPN magnetic response cartilage repair gradient hydrogel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346790A (en) * | 2001-09-26 | 2002-05-01 | 复旦大学 | Process for synthesizing nano-size uniform mesoporous silicon oxide ball separating agent |
| CN1445797A (en) * | 2003-04-01 | 2003-10-01 | 吉林大学 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
-
2007
- 2007-12-06 CN CN2007101718279A patent/CN101205420B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346790A (en) * | 2001-09-26 | 2002-05-01 | 复旦大学 | Process for synthesizing nano-size uniform mesoporous silicon oxide ball separating agent |
| CN1445797A (en) * | 2003-04-01 | 2003-10-01 | 吉林大学 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| Wenru Zhao, et al."Fabrication of Uniform Magnetic Nanocomposite Spheres with a Magnetic Core/Mesoporous Silica Shell Structure".《Journal of American Chemical Society》.2005,(第127期),第8916-8917页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101205420A (en) | 2008-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101205420B (en) | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof | |
| CN103500622B (en) | Magnetism inorganic nanoparticle/ordered mesopore silica nuclear shell composite microsphere and preparing method thereof | |
| CN108711480B (en) | Magnetic mesoporous silica nanochain with core-shell structure and preparation method thereof | |
| Ahangaran et al. | Surface modification of Fe 3 O 4@ SiO 2 microsphere by silane coupling agent | |
| CN101299366B (en) | Magnetic inorganic nano corpuscle/zeolite nucleocapsid type composite microsphere and preparation method thereof | |
| CN110075770B (en) | Magnetic ordered mesoporous carbon-based or polymer-based core-shell structure microsphere and preparation method thereof | |
| Guo et al. | Synthesis and characterization of carbon sphere-silica core–shell structure and hollow silica spheres | |
| CN105126715B (en) | Magnetic mesoporous silica microsphere material with yolk structure and preparing method thereof | |
| CN103223488B (en) | Preparation method for silver-coated silicon dioxide composite microsphere particles | |
| CN107961764B (en) | A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon | |
| CN102989398A (en) | Magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres and preparation method thereof | |
| CN107790075B (en) | Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles | |
| CN103310935A (en) | Silicon dioxide nano magnetic microsphere and preparation method thereof | |
| CN102350281A (en) | Preparation method of fluorescent mesoporous silica-based core-shell nanoscale capsule | |
| CN105694356A (en) | Porous hollow phenolic resin nanospheres and carbon nanospheres and preparation method | |
| CN111204818B (en) | Method for preparing magnetic mesoporous silica particles by using pollen as template | |
| CN103350226B (en) | SiO2/Ag composite micron sphere and preparation method thereof | |
| CN109950014A (en) | A kind of method that weak hydrolyzation system prepares magnetic mesoporous SiO 2 composite microsphere | |
| CN106732221B (en) | A kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure | |
| CN1427041A (en) | Preparation method of spherical composite nano silver/silicon dioxide functional material | |
| JP2013542157A (en) | Production of irregular porous silicon dioxide material and application of fatty alcohol polyoxyethylene ether in its production | |
| CN103559973B (en) | A kind of Fe3O4SiO2Magnetic single hole hollow microsphere and preparation method thereof | |
| CN101236816B (en) | Making method for magnetic kernel medium hole hollow ball | |
| CN104209513B (en) | Superparamagnetic nanometer composite material and preparation method for same | |
| CN101521067A (en) | Core/shell type magnetic particle product and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120118 Termination date: 20151206 |
|
| EXPY | Termination of patent right or utility model |