CN1994879A - Process for preparing mesopore silica dioxide hollow sphere - Google Patents
Process for preparing mesopore silica dioxide hollow sphere Download PDFInfo
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- CN1994879A CN1994879A CN 200610129711 CN200610129711A CN1994879A CN 1994879 A CN1994879 A CN 1994879A CN 200610129711 CN200610129711 CN 200610129711 CN 200610129711 A CN200610129711 A CN 200610129711A CN 1994879 A CN1994879 A CN 1994879A
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Abstract
The invention discloses a making method of dielectric silica hollow microball, which is characterized by the following: adopting emulsion as mould; making silicic acid carbethoxy as silicon source through dispersing controlling self-assembling method (DCSA); setting 3-methoxyl silane as co-structural guide agent; obtaining the product under acid condition with even diameter at 2-5um, specific surface area at 650-900m2/g and total pore bulk at 0.6-0.9cm3/g.
Description
Technical field
The invention belongs to the preparation method of the preparation field of porous material, particularly a kind of mesopore silica dioxide hollow sphere.
Background technology
Mesoporous be between micropore (aperture＜2nm) and macropore (＞50nm) between a kind of aperture.Mesoporous silicon oxide is a kind of cellular solid of aperture in mesoporous scope.The ordered mesoporous silica dioxide material is from scientist (C.T.Kresge, M.E.Leonowicz, the W.J.Roth of Mobil company in 1992, J.C.Vartuli, and J.S.Beck, Nature 1992,359,710.) successfully synthetic since because in catalysis, absorption with wide application prospect (the A.Corma Chem.Rev. that many aspects have such as separate, 1997,97,2373.) people's attention and extremely becomes the focus of Materials science research.
Mesopore silica dioxide hollow sphere wraps up at medicine, drug delivery and slowly-releasing, fields such as artificial cell design and special catalyst assembling design have all shown important use value, and therefore, the synthesizing mesoporous silicon dioxide hollow microsphere causes the attention of scientific circles' height.Chinese patent (CN1792788) adopts the cosurfactant polyvinylpyrrolidone, and preparation has the silicon dioxide hollow sphere of hexagonal phase penetrating mesopore orbit, and a lot of documents also are designed into the preparation of hollow silica microsphere, for example, hard template method (P.M.Arnal, F.Schuth, F.Kleitz, Chem.Comm.2006,1203), vesica method (H.Djojoputro, X.F.Zhou, S.Z.Qiao, L.Z.Wang, C.Z.Yu, G.Q.Lu, J.Am.Chem.Soc.2006,128,6320), micro emulsion method (S.Schacht, Q.Huo, I.G.Voigt-Martin, G.D.Stucky, F.Schuth, Science, 1996,273,768), though these methods can both synthesize hollow microsphere, but the spherical shell of synthetic hollow microsphere all is a kind of mesoscopic structure, and about the synthetic report of the shell multilevel hierarchy of hollow ball seldom (Q.Sun, P.J.Kooyman, J.G.Grossmann, P.H.H.Bomans, P.M.Frederik, P.C.M.M.Magusin, T.P.M.Beelen, R.A.van Santen, N.A.J.M.Sommerdijk, Adv.Mater.2003,15,1097).Because easing up at the medicine parcel of the shell of hollow ball released, the potential application of the preparation of special catalyst and biomineralization mechanism has caused the very big interest of material supply section scholar.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of mesopore silica dioxide hollow sphere, the inventive method technology is simple, good reproducibility, and the productive rate height, cost is low.
It is template that mesopore silica dioxide hollow sphere of the present invention adopts the self stabilization emulsion, prepare by diffusion control self-assembling method (DCSA), with the tetraethoxy is the silicon source, is co-structured directed agents with (3-aminopropyl) Trimethoxy silane, prepares under acidic conditions.
Being characterized as of mesopore silica dioxide hollow sphere of the present invention: mean diameter is 2～5 μ m, productive rate 100%, specific surface 650～900m
2/ g,, total pore volume 0.6-0.9cm
3/ g; Two kinds of mesoporous distributions are arranged, and a kind of is that the worm of spherical shell is mesoporous, and mesoporous aperture is 1.6～4.1nm; Another kind of lamellar phase for the hemi-spherical granule (bud) of growing on the spherical shell is mesoporous, and mesoporous aperture is 6.5～9.6nm.
The step that the preparation method of described mesopore silica dioxide hollow sphere comprises:
1) mol ratio of water, sarcosyl, hydrochloric acid, tetraethoxy and (3-aminopropyl) Trimethoxy silane is 100: 0.04: 0.05: 0.28: 0.023.
2) prepare the aqueous solution that mass percent concentration is 1.0% sarcosyl, hydrochloric acid soln and the tetraethoxy of mol ratio 18 to 1 and the mixing solutions of (3-aminopropyl) Trimethoxy silane of 0.1 mol respectively.
3) under brute force stirs, the hydrochloric acid soln of 0.1 mol is joined in the aqueous solution that mass percent concentration is 1.0% sarcosyl, the pH value of mixing solutions is 2.26; Continue to stir 1 hour; The mixing solutions that adds silicon source tetraethoxy and (3-aminopropyl) Trimethoxy silane then, make that the concentration of tetraethoxy is 0.2 mol in the mixing solutions, the pH value is 4.76, continues to stir 10 minutes, 60～80 ℃ were reacted 2～48 hours, got white precipitate.
4) vacuum filtration, distilled water wash, 50 ℃ of dryings, 550～650 ℃ of roastings 6 hours obtain mesopore silica dioxide hollow sphere.
The mesopore silica dioxide hollow sphere purity height of the inventive method preparation, good dispersity, specific surface area is big, two mesoporous distributions, the character that these are good can be applied to fractionation by adsorption, medicine parcel, medicament slow release, fields such as drug delivery.
The Metaporous silicon dioxide material of the present invention's preparation can be by changing the size of reaction times and controlling reaction temperature hollow ball, the size of bud, the size of two mesoporous aperture sizes and pore volume simply.The mesoporous silicon oxide hollow ball that can prepare different size parameter and aperture parameters as required, this application for the mesoporous silicon oxide hollow ball is very favourable.
The inventive method adopts anion surfactant cheaply, and single-phase static reaction system is simple, the productive rate height, and cost is low, is easy to scale operation.
Description of drawings
The mesopore silica dioxide hollow sphere sem photograph and the transmission electron microscope picture of Fig. 1 embodiment of the invention 1: (a) surface sweeping Electronic Speculum picture (b, c, d) transmission electron microscope picture.
Mesopore silica dioxide hollow sphere nitrogen adsorption/the desorption isotherm and the graph of pore diameter distribution of Fig. 2 embodiment of the invention 1.
The mesopore silica dioxide hollow sphere low-angle scattering of X-rays figure of Fig. 3 embodiment of the invention 1
The transmission electron microscope picture of bud on the mesopore silica dioxide hollow sphere bud of Fig. 4 embodiment of the invention 8
Embodiment
Further describe feature of the present invention below by example, but the present invention is not limited to following example.
(1) the preparation surfactant soln makes that the mass percent of sarcosyl is 1%;
(2) preparation hydrochloric acid soln, the concentration of hydrochloric acid is 0.1 mol;
(3) under brute force stirs, in step (1), add the hydrochloric acid acid solution of preparation in the 12.0mL step (2), continue to stir 1 hour, at this moment, mixing solutions is an oyster white.
(4) the preparation mol ratio is the silicon source solution of 18 to 1 tetraethoxy and (3-aminopropyl) Trimethoxy silane;
(5) stir down, the silicon source 1.5g of preparation in the step (4) is joined in the mixing solutions in the step (3), continue to stir ten minutes, 80 ℃ were reacted 48 hours, get white precipitate, vacuum filtration, distilled water wash, 50 ℃ of dryings, 550 ℃ of roastings 6 hours obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, specific surface 645m
2/ g,, total pore volume 0.78cm
3/ g; Two kinds of mesoporous distributions are arranged, and a kind of is that the worm of spherical shell is mesoporous, and mesoporous aperture is 4.1nm; Another kind of lamellar phase for the hemi-spherical granule (bud) of growing on the spherical shell is mesoporous, and mesoporous aperture is 9.6nm; The size of bud is at 100～500nm on the spherical shell.
Embodiment 2
With embodiment 1,80 ℃ of reaction times in the step (5) are controlled to be 24 hours, other conditions are constant, obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, specific surface 826m
2/ g,, total pore volume 0.91cm
3/ g; Two kinds of mesoporous distributions are arranged, and a kind of is that the worm of spherical shell is mesoporous, and mesoporous aperture is 3.9nm; Another kind of lamellar phase for the hemi-spherical granule (bud) of growing on the spherical shell is mesoporous, and mesoporous aperture is 9.3nm; The size of bud is at 100～500nm on the spherical shell.
Embodiment 3
With embodiment 1,80 ℃ of reaction times in the step (5) are controlled to be 18 hours, other conditions are constant, obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, specific surface 720m
2/ g,, total pore volume 0.77cm
3/ g; Two kinds of mesoporous distributions are arranged, and a kind of is that the worm of spherical shell is mesoporous, and mesoporous aperture is 3.7nm; Another kind of lamellar phase for the hemi-spherical granule (bud) of growing on the spherical shell is mesoporous, and mesoporous aperture is 8.5nm; The size of bud is at 100～500nm on the spherical shell.
Embodiment 4
With embodiment 1,80 ℃ of reaction times in the step (5) are controlled to be 6 hours, other conditions are constant, obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, specific surface 656m
2/ g,, total pore volume 0.61cm
3/ g; Two kinds of mesoporous distributions are arranged, and a kind of is that the worm of spherical shell is mesoporous, and mesoporous aperture is 7.7nm; Another kind of lamellar phase for the hemi-spherical granule (bud) of growing on the spherical shell is mesoporous, and mesoporous aperture is 2.5nm; The size of bud is at 100～500nm on the spherical shell.
Embodiment 5
With embodiment 1,80 ℃ of reaction times in the step (5) are controlled to be 2 hours, other conditions are constant, obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, specific surface 902m
2/ g,, total pore volume 0.72cm
3/ g; Two kinds of mesoporous distributions are arranged, and a kind of is that the worm of spherical shell is mesoporous, and mesoporous aperture is 1.6nm; Another kind of lamellar phase for the hemi-spherical granule (bud) of growing on the spherical shell is mesoporous, and mesoporous aperture is 6.5nm; The size of bud is at 100～500nm on the spherical shell.
Embodiment 6
With embodiment 1, temperature of reaction in the step (5) is controlled to be 60 ℃, the reaction times is 2 hours, other conditions are constant, obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, long on the spherical shell a small amount of budlet, the size of bud are arranged is about 50nm.
Embodiment 7
With embodiment 1, temperature of reaction in the step (5) is controlled to be 60 ℃, the reaction times is 5 hours, other conditions are constant, obtain mesopore silica dioxide hollow sphere, and mean diameter is 2～5 μ m, productive rate 100%, long on the spherical shell a large amount of budlets, the size of bud are arranged is about 50nm.
Embodiment 8
With embodiment 1, temperature of reaction in the step (5) is controlled to be 60 ℃, reaction times is 18 hours, and other conditions are constant, obtain mesopore silica dioxide hollow sphere, mean diameter is 2～5 μ m, productive rate 100%, long on the spherical shell have a large amount of budlets, much all is to sprout on the bud again, multistage bud structure occurs, the size of bud is about 50nm.
Claims (6)
1, a kind of method for preparing mesopore silica dioxide hollow sphere.The step that comprises:
1) mol ratio of water, sarcosyl, hydrochloric acid, tetraethoxy and (3-aminopropyl) Trimethoxy silane is 100: 0.04: 0.05: 0.28: 0.023.
2) prepare the aqueous solution that mass percent concentration is 1.0% sarcosyl, hydrochloric acid soln and the tetraethoxy of mol ratio 18 to 1 and the mixing solutions of (3-aminopropyl) Trimethoxy silane of 0.1 mol respectively.
3) under brute force stirs, the hydrochloric acid soln of 0.1 mol is joined in the aqueous solution that mass percent concentration is 1.0% sarcosyl, the pH value of mixing solutions is 2.26; Continue to stir 1 hour; The mixing solutions that adds silicon source tetraethoxy and (3-aminopropyl) Trimethoxy silane then, make that the concentration of tetraethoxy is 0.2 mol in the mixing solutions, the pH value is 4.76, continues to stir 10 minutes, 60～80 ℃ were reacted 2～48 hours, got white precipitate.
4) vacuum filtration, distilled water wash, 50 ℃ of dryings, 550～650 ℃ of roastings 6 hours obtain mesopore silica dioxide hollow sphere.
2, the method for claim 1 is characterized in that described step 2) in, tensio-active agent is a sarcosyl.
3, the method for claim 1 is characterized in that described step 2) in, the mass percent concentration of sarcosyl is 1.0%.
4, the method for claim 1 is characterized in that described step 2) in, the mol ratio of tetraethoxy and (3-aminopropyl) Trimethoxy silane is 18 to 1.
5, the method for claim 1 is characterized in that in the described step 3), add the hydrochloric acid of 0.1 mol after, the pH value of mixing solutions is 2.26.
6, the method for claim 1 is characterized in that in the described step 3), adds the mixing solutions of silicon source tetraethoxy and (3-aminopropyl) Trimethoxy silane, and the concentration of tetraethoxy is 0.2 mol in the mixing solutions, and the pH value is 4.76.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475184B (en) * | 2009-01-15 | 2010-11-10 | 北京航空航天大学 | Preparation of inorganic magnetic material for filling hollow mesoporous silicon dioxide sphere |
| CN102327622A (en) * | 2011-09-08 | 2012-01-25 | 上海交通大学 | Method for loading siRNA (small interfering Ribonucleic Acid) by using mesoporous silicon dioxide nanoparticles |
| CN102432028A (en) * | 2011-10-08 | 2012-05-02 | 华东理工大学 | Method for preparing silicon dioxide mesoporous spheres with adjustable pore sizes and particle sizes |
| CN102070148B (en) * | 2009-11-23 | 2012-11-07 | 哈尔滨理工大学 | Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 |
| CN103130229A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Multistage pore silica nano material and preparation method thereof |
| CN102050453B (en) * | 2009-11-06 | 2013-10-16 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| CN106675151A (en) * | 2016-11-22 | 2017-05-17 | 常州思宇知识产权运营有限公司 | Preparation method of hierarchical mesoporous silica flatting agent |
| CN114106706A (en) * | 2021-12-24 | 2022-03-01 | 博力思(天津)电子科技有限公司 | Copper interconnection polishing solution with pressure buffering effect and preparation method of abrasive thereof |
| CN115990467A (en) * | 2023-03-16 | 2023-04-21 | 中国科学院兰州化学物理研究所 | Preparation method of high-stability surface radial mesoporous silica microsphere chromatographic packing |
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2006
- 2006-11-29 CN CN 200610129711 patent/CN1994879A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475184B (en) * | 2009-01-15 | 2010-11-10 | 北京航空航天大学 | Preparation of inorganic magnetic material for filling hollow mesoporous silicon dioxide sphere |
| CN102050453B (en) * | 2009-11-06 | 2013-10-16 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| CN102070148B (en) * | 2009-11-23 | 2012-11-07 | 哈尔滨理工大学 | Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 |
| CN102327622B (en) * | 2011-09-08 | 2014-08-06 | 上海交通大学 | Method for loading siRNA (small interfering Ribonucleic Acid) by using mesoporous silicon dioxide nanoparticles |
| CN102327622A (en) * | 2011-09-08 | 2012-01-25 | 上海交通大学 | Method for loading siRNA (small interfering Ribonucleic Acid) by using mesoporous silicon dioxide nanoparticles |
| CN102432028A (en) * | 2011-10-08 | 2012-05-02 | 华东理工大学 | Method for preparing silicon dioxide mesoporous spheres with adjustable pore sizes and particle sizes |
| CN103130229A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Multistage pore silica nano material and preparation method thereof |
| CN103130229B (en) * | 2011-11-30 | 2014-10-22 | 中国科学院大连化学物理研究所 | Multistage pore silica nano material and preparation method thereof |
| CN106675151A (en) * | 2016-11-22 | 2017-05-17 | 常州思宇知识产权运营有限公司 | Preparation method of hierarchical mesoporous silica flatting agent |
| CN114106706A (en) * | 2021-12-24 | 2022-03-01 | 博力思(天津)电子科技有限公司 | Copper interconnection polishing solution with pressure buffering effect and preparation method of abrasive thereof |
| CN114106706B (en) * | 2021-12-24 | 2022-12-20 | 博力思(天津)电子科技有限公司 | Copper interconnection polishing solution with pressure buffering effect and preparation method of abrasive thereof |
| CN115990467A (en) * | 2023-03-16 | 2023-04-21 | 中国科学院兰州化学物理研究所 | Preparation method of high-stability surface radial mesoporous silica microsphere chromatographic packing |
| CN115990467B (en) * | 2023-03-16 | 2024-02-27 | 中国科学院兰州化学物理研究所 | Preparation method of high-stability surface radial mesoporous silica microsphere chromatographic packing |
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