CN102718225A - Preparation method of ordered mesoporous silica microspheres with hollow structures - Google Patents
Preparation method of ordered mesoporous silica microspheres with hollow structures Download PDFInfo
- Publication number
- CN102718225A CN102718225A CN201210248779XA CN201210248779A CN102718225A CN 102718225 A CN102718225 A CN 102718225A CN 201210248779X A CN201210248779X A CN 201210248779XA CN 201210248779 A CN201210248779 A CN 201210248779A CN 102718225 A CN102718225 A CN 102718225A
- Authority
- CN
- China
- Prior art keywords
- mesoporous silica
- hollow structure
- ordered mesoporous
- water
- hollow
- 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.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000003093 cationic surfactant Substances 0.000 claims abstract 5
- 239000011259 mixed solution Substances 0.000 claims abstract 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical group [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 3
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 27
- 239000007787 solid Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000005530 etching Methods 0.000 abstract description 5
- 239000000839 emulsion Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000002607 contrast-enhanced ultrasound Methods 0.000 abstract 1
- 238000012377 drug delivery Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 24
- 238000002156 mixing Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 12
- 241000282326 Felis catus Species 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
本发明公开了一种空心结构的有序介孔二氧化硅微球的制备方法，首先将阳离子表面活性剂溶于乙醇和水的混合溶液，加热搅拌条件下依次向混合溶液中加入氨水和硅源，反应一段时间后获得实心二氧化硅微球；洗涤得到的二氧化硅，并转移至水中刻蚀，反应一段时间后获得空心二氧化硅微球；最后，收集空心二氧化硅，干燥、焙烧获得空心结构的有序介孔二氧化硅微球产品。本发明的制备方法不需要预先制备牺牲硬模板或乳液模板，具有工艺过程简单、反应条件温和、成本低廉、环境友好的特点；制备的空心介孔二氧化硅微球在超声造影、药物传输等生物医学领域具有巨大的应用潜力。
The invention discloses a method for preparing ordered mesoporous silica microspheres with a hollow structure. First, a cationic surfactant is dissolved in a mixed solution of ethanol and water, and ammonia water and silicon dioxide are sequentially added to the mixed solution under heating and stirring conditions. source, after a period of reaction to obtain solid silica microspheres; wash the obtained silica, and transfer to water for etching, and obtain hollow silica microspheres after a period of reaction; finally, collect hollow silica, dry, The ordered mesoporous silica microsphere product with hollow structure is obtained by calcining. The preparation method of the present invention does not require pre-preparation of sacrificial hard templates or emulsion templates, and has the characteristics of simple process, mild reaction conditions, low cost, and environmental friendliness; the prepared hollow mesoporous silica microspheres can be used in contrast-enhanced ultrasound, drug delivery, etc. The field of biomedicine has great application potential.
Description
Technical field
The present invention relates to a kind of preparation method of ordered mesoporous silica dioxide microballoon of hollow structure, belong to the preparation field of inorganic materials.
Background technology
It with the tensio-active agent research focus that the mesoporous material in synthetic high-ratio surface of template and homogeneous aperture has become Materials science.These mesoporous materials have been widely used in physics, chemistry and biomedical sector.Can synthesize multiple mesoporous material through the control reaction conditions with higher structure and special appearance, as: film, fiber, ball, hollow ball etc.Wherein, the mesoporous silicon dioxide micro-sphere that has a hollow structure has caused people's extensive concern because of its particular structural and function.At first, researcher uses O/w emulsion, supercritical CO
2And microcapsule have successfully prepared mesoporous silicon oxide (S. Schacht, Q. Huo, I. G. Voigt-Martin, G. D. Stucky, F. Schuth, Science, 1996,273,768 with hollow structure as hollow template; J. Wang, Y. Xia, W. Wang, M. Poliakoff, R. Mokaya, J. Mater. Chem., 2006,16,1751; P. T. Tanev, T. J. Pinnavaia, Science 1996,271, and 1267).Yet because these soft template have low stability and relatively poor homogeneity in reaction soln, thereby the mesoporous silicon oxide of the hollow structure for preparing has irregular pattern and wide distribution of sizes usually.In addition, adopt the soft template technology to be difficult to realize the regulation and control of cavity size and shell thickness.In order to overcome the deficiency of soft template technology of preparing, people have developed and have utilized polymkeric substance or colloidal inorganic particle to make to sacrifice hard template strategy (Z. Chen, Z.-M. Cui, the F. Niu of template; L. Jiang, W.-G. Song, Chem. Commun.; 2010,46,6524; Y. Zhao, L.-N. Lin, Y. Lu, S.-F. Chen, L. Dong, S.-H. Yu, Adv. Mater. 2010,22,5255; X. Fang, C. Chen, Z. Liu, P. Liu, N. Zheng, Nanoscale, 2011,3,1632).Yet the preparation of sacrificial hard template and removal often relate to the reaction process of a plurality of complicacies, and the preparation process is consuming time, and cost is also higher relatively, is inappropriate for the expansion production of industriallization and commercialization.In addition, because surfactant micelle trend lies low in the surface of sacrificing template reducing surface energy, thereby the mesopore orbit of the hollow ball for preparing is parallel to microsphere surface usually, and this is unfavorable for the transmission of guest molecule in hollow ball shell both sides.
Summary of the invention
Goal of the invention: in order to overcome the deficiency that exists in the prior art, the present invention provides a kind of method of ordered mesoporous silica dioxide microballoon of simple preparation hollow structure.
Technical scheme: for realizing above-mentioned purpose; The preparation method of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention comprises: at first cats product is dissolved in the mixing solutions of second alcohol and water, adding ammoniacal liquor and silicon source make the solid silicon dioxide microsphere with mesoscopic structure in the mixing solutions of the second alcohol and water that contains cats product; And then prepare hollow silica ball through the technological process of simple water etching; Method through roasting is removed the ordered mesoporous silica dioxide microballoon that cats product promptly obtains having the hollow structure in radial duct at last.
The concrete synthesis step of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention is following:
(1) cats product is dissolved in the mixing solutions of second alcohol and water; Under 10～50 ℃, agitation condition, ammoniacal liquor and silicon source are joined in the mixing solutions of cation tensio-active agent; Reaction 3～24 h; Generate white precipitation of silica, the mol ratio of cats product, silicon source, ammoniacal liquor, second alcohol and water is 1:10～40: 30～120: 1000～5000:6000～25300;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions in the water, at 20～90 ℃ of condition held 1～150 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 500～600 ℃ of roasting 5 ~ 7 h, finally obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
As preferably, described cats product is a kind of in Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide or the palmityl trimethyl ammonium chloride.
Described silicon source is a kind of in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters.
The concentration of described silica dispersions is 0.1～5 mg/mL
Described agitation condition is 200～800 rev/mins.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that the employing method for preparing obtains is 200～800 nm; Shell thickness is 25～200 nm; Mesopore orbit is six side's ordered arrangement, and the aperture is 2.5～4.0 nm; The specific surface area of the ordered mesoporous silica dioxide microballoon of described hollow structure is 900～1600 m
2/ g.
Beneficial effect: compared with prior art, the preparation method of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention has the following advantages:
1, the present invention is a template with cats product commonly used, that cost is low, can prepare the ordered mesoporous silica dioxide microballoon of hollow structure through simple technological process;
2, the present invention adopts pure water to synthesize solid silicon-dioxide, and then has characteristics low for equipment requirements, with low cost, eco-friendly through the process that water etching prepares the ordered mesoporous silica dioxide microballoon of hollow structure; The productive rate that adopts the hollow ball that this method prepares is up to 98%, is of value to industriallization and enlarges and produce;
3, can regulate and control the cavity size and the shell thickness of tiny balloon effectively through the temperature and time of regulation and control etching.
Adopt the ordered mesoporous silica dioxide microballoon of the hollow structure that preparation method of the present invention makes, have the following advantages:
1, the ordered mesoporous silica dioxide microballoon of this hollow structure has the spherical morphology and the size of homogeneous; The hollow ball surface has abundant silicon hydroxyl, has good polar solvent dispersing property and biocompatibility; This hollow ball has huge application potential at biomedical sectors such as ultrasonic contrast, medicine transmission;
2, the ordered mesoporous silica dioxide microballoon of this hollow structure has the aperture of high specific surface area, pore volume and homogeneous; Mesopore orbit is six side's ordered arrangement (spacer: P6mm), be radial, help the transmission of medicine equimolecular in the mesoporous lamella both sides;
3, hollow ball shakes in 60 Hz ultrasonic cleaners did not have breakage in 10 minutes, explained that hollow ball has favorable mechanical stability; Morphology change does not take place through 600 ℃ high-temperature roasting in hollow ball, explains that hollow ball has good thermostability.
Description of drawings
The electron micrograph of the silicon-dioxide solid sphere that Fig. 1 the present invention makes under the processing condition of embodiment 1;
The electron micrograph of the ordered mesoporous silica dioxide tiny balloon with hollow structure that Fig. 2 the present invention makes under the processing condition of embodiment 1: in Fig. 2, a is the low power stereoscan photograph of hollow ball; B is for grinding the high power stereoscan photograph of broken hollow ball; C is the transmission electron microscope photo of hollow ball; D is the transmission electron microscope photo of the mesoporous lamella of hollow ball;
The X-ray diffractogram of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 3 the present invention makes under the processing condition of embodiment 1;
Nitrogen adsorption-the desorption isotherm and the pore distribution curve of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 4 the present invention makes under the processing condition of embodiment 1;
The transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 5 the present invention makes under the processing condition of embodiment 4;
The transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 6 the present invention makes under the processing condition of embodiment 5;
The transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 7 the present invention makes under the processing condition of embodiment 6.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done explanation further.
The preparation method of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention; At first cats product is dissolved in the mixing solutions of second alcohol and water; In mixing solutions, add ammoniacal liquor and silicon source under the condition of heating and stirring successively, obtain solid silicon dioxide microsphere after reaction for some time; The silicon-dioxide that washing obtains, and be transferred to etching in the water, obtain the hollow silicon dioxide microballoon after reaction for some time; At last, collect hollow silicon dioxide, dry, roasting obtains the ordered mesoporous silica dioxide microspheres product of hollow structure.This preparation method uses cheap cats product to be template, can prepare the ordered mesoporous silica dioxide microballoon of hollow structure through simple technological process.That the preparation process has is low for equipment requirements, technological process is simple, eco-friendly characteristics.The productive rate of the order mesoporous microballoon of the hollow structure for preparing is of value to industriallization and enlarges production up to 98%.The mesopore orbit of the mesoporous silicon dioxide micro-sphere of the hollow structure that obtains in order, be radial, help the transmission of molecule and ion in the shell both sides.
Embodiment of the present invention is following:
Embodiment 1:
(1) 0.08 g cetyl trimethylammonium bromide is dissolved in the mixing solutions of 30 ml ethanol and 50 ml water, at 30 ℃, under the 500 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive tetraethyl orthosilicate of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere (Fig. 1);
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 50 ℃ of conditions, stir 20 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon (referring to Fig. 2) of hollow structure.
The silicon-dioxide that obtains through step (1) is the solid sphere with spherical morphology.The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 550 nm, has hollow structure, and shell thickness is about 100 nm; It is radial that mesopore orbit is, and has six side's ordered structures (Fig. 3); The aperture with homogeneous (as shown in Figure 4) of mesoporous silicon dioxide micro-sphere, aperture size is 2.6 nm; Specific surface area is 987 m
2/ g.
Embodiment 2:
(1) 0.08 g Trimethyllaurylammonium bromide is dissolved in the mixing solutions of 15 ml ethanol and 100 ml water, at 10 ℃, under the 200 rpm agitation conditions with 0.5 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive tetraethyl orthosilicate of 0.5 ml join in the mixing solutions, react 24 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (0.1 mg/ml) in the water, under 20 ℃ of conditions, stir 1 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 500 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 210 nm, has hollow structure, and shell thickness is about 40 nm; It is radial that mesopore orbit is, and has six side's ordered structures; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.0 nm; Specific surface area is 1124 m
2/ g.
Embodiment 3:
(1) 0.08 g cetyl trimethylammonium bromide is dissolved in the mixing solutions of 60 ml ethanol and 25 ml water, at 50 ℃, under the 500 rpm agitation conditions with 1.9 ml strong aquas (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive tetraethyl orthosilicate of 1.9 ml join in the mixing solutions, react 3 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (5 mg/ml) in the water, under 90 ℃ of conditions, stir 120 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 600 ℃ of roasting 7 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 780 nm, has hollow structure, and shell thickness is about 60 nm; It is radial that mesopore orbit is, and has six side's ordered structures; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 2.5 nm; Specific surface area is 913 m
2/ g.
Embodiment 4:
(1) 0.08 g octadecyl trimethylammonium bromide is dissolved in the mixing solutions of 30 ml ethanol and 50 ml water, at 30 ℃, under the 800 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive quanmethyl silicate of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 25 ℃ of conditions, stir 18 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 5 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 650 nm, has hollow structure, and shell thickness is about 200 nm; It is radial that mesopore orbit is, and has hexagonal structure; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.9 nm; Specific surface area is 987 m
2/ g.Fig. 5 is the transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that makes under the processing condition of present embodiment.
Embodiment 5:
(1) 0.08 g TTAB is dissolved in the mixing solutions of 25 ml ethanol and 60 ml water, at 30 ℃, under the 500 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and positive silicic acid four butyl esters of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 25 ℃ of conditions, stir 144 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 450 nm, has hollow structure, and shell thickness is about 40 nm; It is radial that mesopore orbit is, and has hexagonal structure; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.1 nm; Specific surface area is 1548 m
2/ g.Fig. 6 is the transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that makes under the processing condition of present embodiment.
Embodiment 6:
(1) 0.08 g palmityl trimethyl ammonium chloride is dissolved in the mixing solutions of 28 ml ethanol and 55 ml water, at 30 ℃, under the 500 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive silicic acid orthocarbonate of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 70 ℃ of conditions, stir 6 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 500 nm, has hollow structure, and shell thickness is about 25 nm; It is radial that mesopore orbit is, and has six side's ordered structures; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.4 nm; Specific surface area is 1223 m
2/ g.Fig. 7 is the transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that makes under the processing condition of present embodiment.
The above only is a preferred implementation of the present invention; Be noted that for those skilled in the art; Under the prerequisite that does not break away from the principle of the invention, can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210248779XA CN102718225A (en) | 2012-07-18 | 2012-07-18 | Preparation method of ordered mesoporous silica microspheres with hollow structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210248779XA CN102718225A (en) | 2012-07-18 | 2012-07-18 | Preparation method of ordered mesoporous silica microspheres with hollow structures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102718225A true CN102718225A (en) | 2012-10-10 |
Family
ID=46944136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210248779XA Pending CN102718225A (en) | 2012-07-18 | 2012-07-18 | Preparation method of ordered mesoporous silica microspheres with hollow structures |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102718225A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803573A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of mesoporous silica molecular sieve |
| CN104386699A (en) * | 2014-11-05 | 2015-03-04 | 上海大学 | Method for preparing multi-shell mesoporous silicon oxide nanomaterial by dual-template method |
| CN106009428A (en) * | 2016-05-13 | 2016-10-12 | 电子科技大学 | Silicon dioxide filled PTFE composite and preparing method thereof |
| CN106861631A (en) * | 2017-02-27 | 2017-06-20 | 苏州大学 | Hollow mesoporous silicon dioxide nano microballoon of functionalization and preparation method thereof and the application in Adsorption of Heavy Metals ion |
| CN107320769A (en) * | 2017-07-07 | 2017-11-07 | 东华大学 | A kind of preparation method of the medical 316L stainless steel with surface ordered mesoporous silica dioxide array |
| CN107827118A (en) * | 2017-11-24 | 2018-03-23 | 北京欧美中科学技术研究院 | A kind of preparation method of the adjustable mesoporous silica hollow ball of shell thickness |
| CN108190896A (en) * | 2018-01-20 | 2018-06-22 | 陕西科技大学 | A kind of preparation method of order mesoporous nano silica microsphere |
| CN108686084A (en) * | 2018-08-13 | 2018-10-23 | 临沂大学 | A kind of oral administration solid self-emulsifying dispersion for treating livestock and birds respiratory disease |
| CN109796019A (en) * | 2019-02-21 | 2019-05-24 | 华中科技大学 | A kind of hollow silicon dioxide nanosphere and its preparation method and application |
| CN110526251A (en) * | 2019-08-28 | 2019-12-03 | 贵州大学 | A kind of preparation method of lithium battery silica negative electrode material |
| CN111013507A (en) * | 2019-12-31 | 2020-04-17 | 南京大学盐城环保技术与工程研究院 | Metal-doped hollow silica microsphere and preparation method and application thereof |
| CN111317825A (en) * | 2020-03-06 | 2020-06-23 | 南京市江宁医院 | Regularly folded ultra-small-size large-pore inorganic silicon macromolecular drug carrier, and preparation method and application thereof |
| CN112999364A (en) * | 2021-03-15 | 2021-06-22 | 武汉理工大学 | Preparation method of hollow mesoporous silica dual-drug sustained-release microspheres for treating osteoporosis |
| CN113104855A (en) * | 2021-04-30 | 2021-07-13 | 武汉大学 | Preparation method of spherical silica |
| CN114468353A (en) * | 2022-03-01 | 2022-05-13 | 湖北中烟工业有限责任公司 | Thermosensitive response essence slow-release microcapsule and preparation method and application thereof |
| CN115924924A (en) * | 2022-08-23 | 2023-04-07 | 河南大学 | Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof |
| CN116120834A (en) * | 2022-12-29 | 2023-05-16 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of closed porous flexible antireflection layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486929A (en) * | 2003-08-12 | 2004-04-07 | 上海交通大学 | Preparation method of mesoporous silica spherical nanoparticles |
| CN102275936A (en) * | 2011-06-09 | 2011-12-14 | 华东师范大学 | Preparation method of mesoporous spherical Sio2 nanoparticles |
-
2012
- 2012-07-18 CN CN201210248779XA patent/CN102718225A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486929A (en) * | 2003-08-12 | 2004-04-07 | 上海交通大学 | Preparation method of mesoporous silica spherical nanoparticles |
| CN102275936A (en) * | 2011-06-09 | 2011-12-14 | 华东师范大学 | Preparation method of mesoporous spherical Sio2 nanoparticles |
Non-Patent Citations (1)
| Title |
|---|
| 滕兆刚: "介孔SiO2及介孔磁性复合物的制备与性质研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803573A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of mesoporous silica molecular sieve |
| CN103803573B (en) * | 2012-11-07 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of preparation method of mesoporous silica molecular sieve |
| CN104386699A (en) * | 2014-11-05 | 2015-03-04 | 上海大学 | Method for preparing multi-shell mesoporous silicon oxide nanomaterial by dual-template method |
| CN104386699B (en) * | 2014-11-05 | 2016-02-17 | 上海大学 | Method for preparing multi-shelled mesoporous silica nanomaterials by double-template method |
| CN106009428A (en) * | 2016-05-13 | 2016-10-12 | 电子科技大学 | Silicon dioxide filled PTFE composite and preparing method thereof |
| CN106009428B (en) * | 2016-05-13 | 2018-02-13 | 电子科技大学 | A kind of silica-filled PTFE composite and preparation method thereof |
| CN106861631A (en) * | 2017-02-27 | 2017-06-20 | 苏州大学 | Hollow mesoporous silicon dioxide nano microballoon of functionalization and preparation method thereof and the application in Adsorption of Heavy Metals ion |
| CN106861631B (en) * | 2017-02-27 | 2020-11-17 | 苏州大学 | Functionalized hollow mesoporous silica nano microsphere, preparation method thereof and application thereof in adsorption of heavy metal ions |
| CN107320769A (en) * | 2017-07-07 | 2017-11-07 | 东华大学 | A kind of preparation method of the medical 316L stainless steel with surface ordered mesoporous silica dioxide array |
| CN107827118A (en) * | 2017-11-24 | 2018-03-23 | 北京欧美中科学技术研究院 | A kind of preparation method of the adjustable mesoporous silica hollow ball of shell thickness |
| CN108190896A (en) * | 2018-01-20 | 2018-06-22 | 陕西科技大学 | A kind of preparation method of order mesoporous nano silica microsphere |
| CN108190896B (en) * | 2018-01-20 | 2021-08-10 | 陕西科技大学 | Preparation method of ordered mesoporous nano-silica microspheres |
| CN108686084A (en) * | 2018-08-13 | 2018-10-23 | 临沂大学 | A kind of oral administration solid self-emulsifying dispersion for treating livestock and birds respiratory disease |
| CN109796019A (en) * | 2019-02-21 | 2019-05-24 | 华中科技大学 | A kind of hollow silicon dioxide nanosphere and its preparation method and application |
| CN109796019B (en) * | 2019-02-21 | 2020-12-15 | 华中科技大学 | A kind of hollow silica nanosphere and its preparation method and application |
| CN110526251A (en) * | 2019-08-28 | 2019-12-03 | 贵州大学 | A kind of preparation method of lithium battery silica negative electrode material |
| CN111013507B (en) * | 2019-12-31 | 2021-12-28 | 南京大学盐城环保技术与工程研究院 | Metal-doped hollow silica microsphere and preparation method and application thereof |
| CN111013507A (en) * | 2019-12-31 | 2020-04-17 | 南京大学盐城环保技术与工程研究院 | Metal-doped hollow silica microsphere and preparation method and application thereof |
| CN111317825A (en) * | 2020-03-06 | 2020-06-23 | 南京市江宁医院 | Regularly folded ultra-small-size large-pore inorganic silicon macromolecular drug carrier, and preparation method and application thereof |
| CN111317825B (en) * | 2020-03-06 | 2021-08-24 | 南京市江宁医院 | Regularly folded ultra-small size macroporous inorganic silicon macromolecular drug carrier, its preparation method and its application |
| CN112999364A (en) * | 2021-03-15 | 2021-06-22 | 武汉理工大学 | Preparation method of hollow mesoporous silica dual-drug sustained-release microspheres for treating osteoporosis |
| CN112999364B (en) * | 2021-03-15 | 2022-06-17 | 武汉理工大学 | Preparation method of hollow mesoporous silica double-drug sustained-release microspheres for osteoporosis treatment |
| CN113104855A (en) * | 2021-04-30 | 2021-07-13 | 武汉大学 | Preparation method of spherical silica |
| CN113104855B (en) * | 2021-04-30 | 2022-03-15 | 武汉大学 | Preparation method of spherical silica |
| CN114468353A (en) * | 2022-03-01 | 2022-05-13 | 湖北中烟工业有限责任公司 | Thermosensitive response essence slow-release microcapsule and preparation method and application thereof |
| CN115924924A (en) * | 2022-08-23 | 2023-04-07 | 河南大学 | Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof |
| CN116120834A (en) * | 2022-12-29 | 2023-05-16 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of closed porous flexible antireflection layer |
| CN116120834B (en) * | 2022-12-29 | 2024-06-11 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of closed porous flexible antireflection layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102718225A (en) | Preparation method of ordered mesoporous silica microspheres with hollow structures | |
| CN102050453B (en) | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material | |
| CN104692399B (en) | Highly-ordered radial spherical crinkled mesoporous silicon dioxide material and preparation method thereof | |
| CN104291385B (en) | Cobalt acid nickel mesoporous microsphere and preparation method thereof | |
| CN101683983B (en) | Method for preparing hollow mesoporous lamella spherical silica material | |
| CN102153094B (en) | Method for preparing ordered mesoporous hollow silica spheres | |
| CN108190896B (en) | Preparation method of ordered mesoporous nano-silica microspheres | |
| CN103011182B (en) | Synthesis method of vesicular mesoporous silicon dioxide | |
| CN104909378B (en) | A kind of preparation method of monodisperse porous silicon dioxide microsphere | |
| CN105329905B (en) | The preparation method of hollow mesoporous silica nano-particle | |
| CN104445214A (en) | Mesoporous silica nano hollow sphere and preparation method thereof | |
| CN102515173A (en) | Method for preparing mesoporous SBA-15 unstuck micro spheres | |
| CN102849750B (en) | Mesoporous silica with radial tunnels and preparation method thereof | |
| CN113548684B (en) | Mesoporous alumina-based core-shell composite material and single micelle guiding interface assembly method and application thereof | |
| CN105110343B (en) | Method for rapid preparation of monodisperse ordered mesoporous silicon oxide hollow sphere | |
| CN106237993A (en) | A preparation method of Fe3O4@MOF‑199@C18 nanocomposite | |
| CN109574507A (en) | A kind of nano-level sphere bioactivity glass and preparation method thereof | |
| CN101817530B (en) | Method for preparing hollow silicon dioxide microspheres | |
| CN102020283A (en) | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter | |
| CN103130229B (en) | Multistage pore silica nano material and preparation method thereof | |
| CN103030134A (en) | Ordered mesoporous carbon-zirconium dioxide composite and preparation method thereof | |
| CN103964449B (en) | Constant pressure and dry technology is utilized to prepare the method for silica aerogel microballoon fast | |
| CN108455862A (en) | A kind of preparation method and application of hollow mesoporous bioglass microballoon | |
| CN104707653B (en) | A kind of novel polystyrene sulfonate-oxidation silicon hybridization solid acid catalyst and preparation method | |
| CN104892874B (en) | Ordered mesoporous polymer nanosphere, its preparation method and application with flexure type duct |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121010 |