CN103011182A - Synthesis method of vesicular mesoporous silicon dioxide - Google Patents
Synthesis method of vesicular mesoporous silicon dioxide Download PDFInfo
- Publication number
- CN103011182A CN103011182A CN201210556813XA CN201210556813A CN103011182A CN 103011182 A CN103011182 A CN 103011182A CN 201210556813X A CN201210556813X A CN 201210556813XA CN 201210556813 A CN201210556813 A CN 201210556813A CN 103011182 A CN103011182 A CN 103011182A
- Authority
- CN
- China
- Prior art keywords
- mesoporous silicon
- sds
- ctab
- silicon oxide
- teos
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000377 silicon dioxide Substances 0.000 title abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 title description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 25
- 238000010189 synthetic method Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000009415 formwork Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000012377 drug delivery Methods 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 abstract 1
- 230000002431 foraging effect Effects 0.000 abstract 1
- 238000009512 pharmaceutical packaging Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 239000013335 mesoporous material Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000009416 shuttering Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000004064 cosurfactant Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Landscapes
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明涉及一种囊泡状介孔二氧化硅的合成方法，按质量比SDS:CTAB:TEOS:H2O=1：(2.2-2.4)：(15.5-16.0)：100称取CTAB、SDS、TEOS、去离子水；将十二烷基硫酸钠和十六烷基三甲基溴化铵先后溶解在去离子水中形成白色溶液，搅拌2-3h后，在搅拌状态下加入正硅酸乙酯，15-25℃继续搅拌24h，然后转移到聚四氟乙烯高压水热釜中100℃条件下老化24h，将反应物抽滤、水洗、室温干燥，在550℃空气氛围中煅烧6h得到目标产物。本发明合成方法简单，反应温度温和，制得的介孔二氧化硅具有单室囊泡的骨架结构，呈现空心球或颗粒状形貌，孔径分布在200-400nm范围内，可以应用于吸附分离，药物包裹，药物缓释和药物传输等领域。
The invention relates to a method for synthesizing vesicular mesoporous silica. CTAB and SDS are weighed according to the mass ratio SDS:CTAB:TEOS:H 2 O=1:(2.2-2.4):(15.5-16.0):100 , TEOS, deionized water; Dissolve sodium lauryl sulfate and cetyltrimethylammonium bromide in deionized water successively to form a white solution, after stirring for 2-3 hours, add ethyl orthosilicate Esters, continue to stir at 15-25°C for 24h, then transfer to a polytetrafluoroethylene high-pressure hydrothermal kettle for aging at 100°C for 24h, filter the reactant with suction, wash with water, dry at room temperature, and calcinate at 550°C for 6h in an air atmosphere to obtain the target product. The synthesis method of the invention is simple, the reaction temperature is mild, and the prepared mesoporous silica has a skeleton structure of unicellular vesicles, presents a hollow spherical or granular shape, and the pore size distribution is in the range of 200-400nm, which can be applied to adsorption and separation , drug packaging, drug sustained release and drug delivery and other fields.
Description
Technical field
The present invention relates to a kind of synthetic method by anionic-cationic surfactant mixed system synthesizing new vesica shape mesoporous silicon oxide, belong to field of material synthesis technology.
Background technology
Scientists from U.S. Mobil company is used the nanostructure self-assembling technique first, synthetic take quaternary cationics as template had since the MCM-41 mesoporous material of adjustable aperture, the preparation of mesoporous material and just caused people's extensive concern in the application in each field.Utilize the ordered mesoporous material of tensio-active agent composite shuttering preparation, because having higher specific surface area, larger pore volume and the adjustable pore passage structure of homogeneous, physical adsorption or new chemically modified can be carried out in its surface, duct, form new functional materials by fixing some functional moleculars, therefore, it is widely used in the embedding of fixing and absorption, biocatalysis, medicine of enzyme and controlled release, sensor field.
Both at home and abroad the mesoporous material of report is M41S series the earliest, and broad research has SBA, MAU, a MAS series etc. in recent years.Vesica shape mesoporous silicon oxide also has stronger physical strength, higher thermostability and hydrothermal stability, so attracted a large amount of related science men to the research interest of this material except the characteristic with general mesoporous material.Preparation vesica shape mesoporous material can the selective polymer microballoon, water-in-oil emulsion is made template, also can utilize different tensio-active agents to make template.The bibliographical information that for example has is crossed with single tensio-active agent and is prepared vesica shape mesoporous silicon oxide (RanaRK as template, MastaiY, Gedanken A.Adv.Mater., 2002,14 (19): 1414-1418), the report that also has standby vesica shape mesoporous silicon oxide (the Yang B of composite shuttering legal system, Edler K, Guo C, Liu H Z.Microporous Mesoporous Mater., 2010,131 (1-3): 21-27).By various research reports, tensio-active agent with special construction particularly compound system of segmented copolymer and cationic and anionic surfactant is made template, more syntheticly have high specific surface area, than macropore volume with than the thick-layer spacing, than the vesica shape Metaporous silicon dioxide material of heat-flash stability and hydrothermal stability.Special its shown great attention in multi-field widespread use such as bio-imaging, sensor, medicine controlled releasing, optical memory and light collector etc., becomes one of study hotspot.
Patent CN101638238A discloses the preparation method of the controlled silica nano material that contains ordered mesoporous pore canals of a kind of pattern and structure, the method may further comprise the steps: 1). and get 0.1～0.3 gram cetyl trimethylammonium bromide and be dissolved in 80～110 ml distilled waters, stir and form uniform solution; 2). be the sodium hydroxide solution of 5 mol/L with 0.2～0.4 ml concn, join step 1) in the solution that obtains, rapid stirring forms transparent colourless solution; 3). 0～0.2 gram Aerosol OT is joined step 2) in the solution that obtains, being warming up to 75～85 degrees centigrade, rapid stirring forms transparent colourless solution, obtains stable system; 4). 1～2 milliliter of tetraethoxysilane is joined step 3) in the solution that obtains, stirring reaction; 5). with step 4) product that obtains filters, washing, and at 60～80 degrees centigrade air drying; 6). with step 5) product that obtains calcines under 500～600 degrees centigrade condition, obtains the controlled silica nano material that contains ordered mesoporous pore canals of pattern and structure.The vesica that this patent system gets is less, and hole wall is thinner, and needs to prepare under 75～85 degrees celsius.
Patent CN101786639A discloses a kind of mesoporous silica molecular sieve and preparation method thereof.Concrete synthesis step is: be (0.01～0.1) with nonionogenic tenside, silicon source, your ratio of hydromassage 1): (300～500): mix (1～3), with acid pH is transferred to 1.0～3.0, formed collosol intermixture in 1～3 hour 20～80 ℃ of lower stirrings; 2) collosol intermixture that obtains of step 1 adds alkaline buffer solution under stirring at room, and regulator solution pH value to 5～7.5 namely obtain white precipitation of silica; 3) roasting under 500～600 ℃ of high temperature of the precipitated product in the step 2 was namely obtained white mesoporous silicon dioxide after 3～5 hours.This patent provides green biomimetic synthesis method, is to make masterplate synthesizing mesoporous silicon dioxide material with single nonionogenic tenside, needs to add cosurfactant and solubility promoter.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method by anionic-cationic surfactant mixed system synthetic capsular blister mesoporous silicon oxide, the method technique is simple, need not to add cosurfactant and solubility promoter, good reproducibility, cost is low, can obtain the larger vesica of pattern.
The technical scheme that the present invention takes is:
A kind of synthetic method of vesica shape mesoporous silicon oxide comprises that step is as follows:
(1) changes in mass ratio SDS:CTAB:TEOS:H into
2O=1:(2.2-2.4): (15.5-16.0): 100 take by weighing cetyl trimethylammonium bromide CTAB, sodium lauryl sulphate SDS, tetraethoxy TEOS, deionized water;
(2) sodium lauryl sulphate and cetyl trimethylammonium bromide successively are dissolved in form white solution in the deionized water, after stirring 2-3h, add tetraethoxy (concentration is not less than 98%) at whipped state (in 350 – 370rpm scopes), 24h is stirred in 30 ℃ of continuation of 20 –, then transfers to the 24h that wears out under 120 ℃ of conditions of 90 – in the tetrafluoroethylene high pressure water heating kettle;
(3) with reactant suction filtration, washing, drying at room temperature, calcining 5-7h removes organic formwork agent CTAB and SDS in 500-600 ℃ the high temperature air atmosphere, and the white powder solid that obtains is target product.
The vesica shape mesoporous silicon oxide of the present invention's preparation is take tetraethoxy (TEOS) as the organosilicon source, and cationicsurfactants and anion surfactant SDS are composite shuttering, prepare under neutrallty condition by hydrothermal method.The mesoporous silicon oxide pattern that makes is larger vesica, and mean pore size is at 200 – 400nm, and hole wall approximately is to be made of the silicon dioxide layer that approximately 10nm is thick; Surface deposition one deck size is about the small-sized Nano particles of silicon dioxide of 20-40nm.
The synthetic method that the invention has the beneficial effects as follows vesica shape Metaporous silicon dioxide material is simple, and temperature of reaction is gentle, and the mesoporous silicon oxide that makes has the skeleton structure of unilamellar vesicle, presents hollow ball or particulate state pattern, and pore size distribution is in the 200-400nm scope.The character that these are good can be applied to fractionation by adsorption, medicine parcel, the fields such as medicament slow release and drug delivery.
The vesica shape mesoporous silicon oxide of the present invention preparation can be by changing experiment condition simply, stirring velocity for example, and the pH value of the addition sequence of masterplate agent or solution is regulated and control size and the pattern of mesoporous material.The present invention has synthesized wide-aperture thermally-stabilised vesica shape mesoporous silicon oxide with this simple hydrothermal method.
Description of drawings
The transmission electron microscope picture (TEM) of the vesica shape mesoporous silicon oxide of preparation in Fig. 1 embodiment of the invention 1; A is low multiple figure, and B is the high multiple figure of single vesica shape mesoporous silicon oxide.
The field emission scanning electron microscope figure (FESEM) of the vesica shape mesoporous silicon oxide that preparation forms in Fig. 2 embodiment of the invention 1.
The small angle X-ray diffraction figure (SAXRD) of the vesica shape mesoporous silicon oxide that preparation forms in Fig. 3 embodiment of the invention 1.
The vesica shape mesoporous silicon oxide SAXRD figure that preparation forms in Fig. 4 embodiment of the invention 2.
The TEM figure of the New Type of Mesoporous silicon-dioxide that preparation forms in Fig. 5 embodiment of the invention 4.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.
Embodiment 1:
(1) takes by weighing respectively the solid surfactant powder of 0.13-0.14g SDS and 0.306g CTAB.
(2) in the beaker of 100ml, take by weighing the 13.3-13.5g deionized water.
(3) low whipping speed is under the condition of 350-370rpm, successively adds two kinds of tensio-active agents that take by weighing in the step (1) in step (2), continues to stir 2 – 3h, and this moment, mixing solutions was milky white solution.
(4) in small beaker, take by weighing the TEOS solution of 2.1-2.2g, under improving stirring velocity state (450rpm), dropwise join in the oyster white mixing solutions of formation in step (3).Be added dropwise to complete rear reduction stirring velocity and under 25 ℃ of conditions, continue to stir 24h, then transfer to the 24h that under 100 ℃ of conditions, wears out in the tetrafluoroethylene high pressure water heating kettle.
(5) with reactant suction filtration, washing, drying at room temperature, in 550 ℃ of air atmosphere, remove organic formwork agent CTAB and SDS with DRZ-4 type tube type resistance furnace calcining 6h, the white powder solid that obtains is target product.Then use transmission electron microscope observing, such as Figure 1A and B, the vesica shape mesoporous silicon oxide of observing preparation is unilocular sporangium blister skeleton structure, and the aperture is dispersed in the 200-400nm scope, and the vesica wall is to be made of the silicon dioxide layer that approximately 10nm is thick; The surface also deposits one deck size and is about the small-sized Nano particles of silicon dioxide of 20 – 40nm.
Embodiment 2:
With embodiment 1, change tensio-active agent addition sequence in the step (3) into simultaneously adding, other conditions are constant, obtain vesica shape mesoporous silicon oxide, mean pore size 200-400nm, deposition preparing spherical SiO 2 nanoparticle on the vesica shape spherical shell.
Embodiment 3:
With embodiment 1, the stirring velocity in the step (3) is changed in the 430 – 460rpm scopes, other conditions are constant, and the appearance of the vesica shape mesoporous silicon oxide that obtains is similar to Example 1.
Embodiment 4:
With embodiment 1, the deionized water in the step (2) is changed into the phosphate buffer soln of pH=8, other conditions are constant, and the appearance of the mesoporous silicon oxide that obtains and embodiment 1 difference are larger, and the globosity (Fig. 5) of thorn-like projection is arranged for the surface.
Take cationicsurfactants and anion surfactant SDS as composite mould plate agent, TEOS is the organosilicon source in a word, and the vesica of spontaneous formation in the aqueous solution utilizes hydrothermal synthesis method to prepare mesopore silicon dioxide nano material.By characterization methods such as FESEM, TEM, SAXRD, synthetic material has been carried out phenetic analysis, the result shows that the earth silicon material that is synthesized is unilocular sporangium blister mesoporous silicon oxide.
Claims (3)
1. the synthetic method of a vesica shape mesoporous silicon oxide is characterized in that, comprises that step is as follows:
(1) SDS:CTAB:TEOS:H in mass ratio
2O=1:2.2-2.4:15.5-16.0:100 takes by weighing cetyl trimethylammonium bromide CTAB, sodium lauryl sulphate SDS, tetraethoxy TEOS, deionized water;
(2) sodium lauryl sulphate and cetyl trimethylammonium bromide successively are dissolved in form white solution in the deionized water, after stirring 2-3h, add tetraethoxy at whipped state, 24h is stirred in 30 ℃ of continuation of 20 –, then transfers to the 24h that wears out under 120 ℃ of conditions of 90 – in the tetrafluoroethylene high pressure water heating kettle;
(3) with reactant suction filtration, washing, drying at room temperature, calcining 5-7h removes organic formwork agent CTAB and SDS in 500-600 ℃ the high temperature air atmosphere, and the white powder solid that obtains is target product.
2. the synthetic method of a kind of vesica shape mesoporous silicon oxide according to claim 1 is characterized in that, the described stirring velocity of step (2) is in the 350-370rpm scope.
3. the synthetic method of a kind of vesica shape mesoporous silicon oxide according to claim 1, it is characterized in that: the described calcining instrument of step (3) is DRZ-4 type tube type resistance furnace, need to calcine 5-7h in the temperature range of 600 ℃ of 500 –.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210556813.XA CN103011182B (en) | 2012-12-20 | 2012-12-20 | Synthesis method of vesicular mesoporous silicon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210556813.XA CN103011182B (en) | 2012-12-20 | 2012-12-20 | Synthesis method of vesicular mesoporous silicon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103011182A true CN103011182A (en) | 2013-04-03 |
| CN103011182B CN103011182B (en) | 2015-03-11 |
Family
ID=47960364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210556813.XA Active CN103011182B (en) | 2012-12-20 | 2012-12-20 | Synthesis method of vesicular mesoporous silicon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103011182B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787345A (en) * | 2014-01-23 | 2014-05-14 | 齐鲁工业大学 | Multilayer vesicular mesoporous silicon dioxide with adjustable number of layers and synthetic method thereof |
| CN103922347A (en) * | 2014-03-29 | 2014-07-16 | 清华大学 | Continuous silica aggregate lipsome material and preparation method thereof |
| 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 |
| CN104876223A (en) * | 2015-05-04 | 2015-09-02 | 河南师范大学 | Preparation method of egg shell type silicon dioxide micro-sphere |
| CN104891511A (en) * | 2015-05-25 | 2015-09-09 | 华东师范大学 | Method for synthesizing mesoporous silicon dioxide nanoparticles by using alkali-free method |
| CN105236417A (en) * | 2015-11-06 | 2016-01-13 | 齐鲁工业大学 | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica |
| CN107115773A (en) * | 2017-06-23 | 2017-09-01 | 深圳华明环保科技有限公司 | A kind of Modified Urea denitrfying agent and preparation method thereof |
| CN108017065A (en) * | 2018-01-10 | 2018-05-11 | 山东科技大学 | A kind of preparation method using the penetrating shape liquid crystal of two dimension as the mesoporous silicon oxide of masterplate |
| CN108217662A (en) * | 2018-01-10 | 2018-06-29 | 山东科技大学 | The template structure and preparation method of a kind of mesoporous silicon oxide with two-dimentional permeable structures |
| CN111924851A (en) * | 2020-09-28 | 2020-11-13 | 上海千溯生物科技有限公司 | A kind of silica nanomaterial with umbrella-like dendritic structure and preparation method thereof |
| CN112156730A (en) * | 2020-08-25 | 2021-01-01 | 安徽壹石通材料科技股份有限公司 | Preparation method of high-purity monodisperse porous silicon oxide spheres |
| CN113651331A (en) * | 2021-07-28 | 2021-11-16 | 扬州大学 | A kind of flower-like mesoporous silica nanoparticle and its preparation method and application |
| CN114106394A (en) * | 2021-11-23 | 2022-03-01 | 清华大学 | A kind of benzene ring bridged organosilicon continuous aggregate vesicle material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264892A (en) * | 2008-04-15 | 2008-09-17 | 中国科学院山西煤炭化学研究所 | A preparation method of double-channel mesoporous silica hollow spheres |
-
2012
- 2012-12-20 CN CN201210556813.XA patent/CN103011182B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264892A (en) * | 2008-04-15 | 2008-09-17 | 中国科学院山西煤炭化学研究所 | A preparation method of double-channel mesoporous silica hollow spheres |
Non-Patent Citations (2)
| Title |
|---|
| CUICUI WU ET AL: "Active biocatalysts based on Candida rugosa lipase immobilized in vesicular silica", 《PROCESS BIOCHEMISTRY》 * |
| CUICUI WU ET AL: "Immobilization of Porcine pancreatic Lipase on Vesicle-like Silica Material with Large Pore", 《ADVANCED MATERIALS RESEARCH》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787345A (en) * | 2014-01-23 | 2014-05-14 | 齐鲁工业大学 | Multilayer vesicular mesoporous silicon dioxide with adjustable number of layers and synthetic method thereof |
| CN103787345B (en) * | 2014-01-23 | 2015-06-17 | 齐鲁工业大学 | Multilayer vesicular mesoporous silicon dioxide with adjustable number of layers and synthetic method thereof |
| CN103922347A (en) * | 2014-03-29 | 2014-07-16 | 清华大学 | Continuous silica aggregate lipsome material and preparation method thereof |
| CN103922347B (en) * | 2014-03-29 | 2015-10-28 | 清华大学 | Continuous aggregate vesicle material of a kind of silicon-dioxide and preparation method thereof |
| 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 |
| CN104876223A (en) * | 2015-05-04 | 2015-09-02 | 河南师范大学 | Preparation method of egg shell type silicon dioxide micro-sphere |
| CN104891511A (en) * | 2015-05-25 | 2015-09-09 | 华东师范大学 | Method for synthesizing mesoporous silicon dioxide nanoparticles by using alkali-free method |
| CN105236417A (en) * | 2015-11-06 | 2016-01-13 | 齐鲁工业大学 | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica |
| CN105236417B (en) * | 2015-11-06 | 2017-03-22 | 齐鲁工业大学 | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica |
| CN107115773A (en) * | 2017-06-23 | 2017-09-01 | 深圳华明环保科技有限公司 | A kind of Modified Urea denitrfying agent and preparation method thereof |
| CN107115773B (en) * | 2017-06-23 | 2020-06-30 | 深圳华明环保科技有限公司 | Modified urea denitration agent and preparation method thereof |
| CN108017065A (en) * | 2018-01-10 | 2018-05-11 | 山东科技大学 | A kind of preparation method using the penetrating shape liquid crystal of two dimension as the mesoporous silicon oxide of masterplate |
| CN108217662A (en) * | 2018-01-10 | 2018-06-29 | 山东科技大学 | The template structure and preparation method of a kind of mesoporous silicon oxide with two-dimentional permeable structures |
| CN112156730A (en) * | 2020-08-25 | 2021-01-01 | 安徽壹石通材料科技股份有限公司 | Preparation method of high-purity monodisperse porous silicon oxide spheres |
| CN112156730B (en) * | 2020-08-25 | 2022-05-03 | 安徽壹石通材料科技股份有限公司 | Preparation method of high-purity monodisperse porous silicon oxide spheres |
| CN111924851A (en) * | 2020-09-28 | 2020-11-13 | 上海千溯生物科技有限公司 | A kind of silica nanomaterial with umbrella-like dendritic structure and preparation method thereof |
| CN111924851B (en) * | 2020-09-28 | 2020-12-25 | 上海千溯生物科技有限公司 | Silicon dioxide nano material with umbrella-shaped dendritic structure and preparation method thereof |
| CN113651331A (en) * | 2021-07-28 | 2021-11-16 | 扬州大学 | A kind of flower-like mesoporous silica nanoparticle and its preparation method and application |
| CN113651331B (en) * | 2021-07-28 | 2023-09-22 | 扬州大学 | Flower-shaped mesoporous silica nanoparticles and preparation method and application thereof |
| CN114106394A (en) * | 2021-11-23 | 2022-03-01 | 清华大学 | A kind of benzene ring bridged organosilicon continuous aggregate vesicle material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103011182B (en) | 2015-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103011182A (en) | Synthesis method of vesicular mesoporous silicon dioxide | |
| CN104129791B (en) | Containing radial mesopore orbit structure spherical silicon dioxide material and preparation method thereof | |
| Guo et al. | Hollow mesoporous silica nanoparticles for intracellular delivery of fluorescent dye | |
| Lootens et al. | Facetted hollow silica vesicles made by templating catanionic surfactant vesicles | |
| CN101387019A (en) | Preparation method of mesoporous silica molecular sieve fiber | |
| CN103663478A (en) | Preparation method of mesoporous silica spherical nano particles with dendritic pore structure | |
| CN104860320A (en) | Method for preparing modified nanosilicon dioxide | |
| CN103011177B (en) | A kind of preparation method of mesopore silicon dioxide nano material | |
| CN104445214A (en) | Mesoporous silica nano hollow sphere and preparation method thereof | |
| CN101168440B (en) | Silicon oxide mesoporous material and preparing method thereof | |
| US20020197206A1 (en) | Mesoporous compositions and method of preparation | |
| KR20130011505A (en) | Method for large-scale production of uniform-sized silica nanoparticles | |
| CN107381659A (en) | The method that template prepares aspherical hollow structure nanocages composite | |
| CN103110952A (en) | Microwave-assisted preparation method of hydroxylapatite nanometer structure porous microspheres | |
| Ha et al. | Periodic Mesoporous Organosilicas | |
| CN104909378A (en) | Preparation method of monodisperse porous silicon dioxide microspheres | |
| CN102515173A (en) | Method for preparing mesoporous SBA-15 unstuck micro spheres | |
| ES2728252T3 (en) | Use of silicon oxide based material for the modified release of biologically active agents | |
| CN104624129A (en) | Preparation method of starch nanometer microspheres based on ionic liquid-type surfactant microemulsion system | |
| CN103495178A (en) | Preparation method of zein/calcium carbonate composite particles and application of zein/calcium carbonate composite particles as drug carriers | |
| JP2013542157A (en) | Production of irregular porous silicon dioxide material and application of fatty alcohol polyoxyethylene ether in its production | |
| CN104386700A (en) | Method for preparing mesoporous silicon dioxide microspheres | |
| CN103833040A (en) | Preparation methods of hollow mesoporous silicon oxide spheres and hollow mesoporous organosilicone spheres | |
| CN101007634A (en) | Hollow silicon gel nano powder material and its preparation method | |
| CN105236417A (en) | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 250353 Shandong, Changqing, West New Town University Science Park Applicant after: Qilu University of Technology Address before: 250353 Shandong, Changqing, West New Town University Science Park Applicant before: Shandong Institute of Light Industry |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SHANDONG INSTITUTE OF LIGHT INDUSTRY TO: QILU UNIVERSITY OF TECHNOLOGY |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201230 Address after: No.18, Songjiang Road, Yancheng Economic Development Zone, Jiangsu Province 224000 Patentee after: JIANGSU CHENGTIAN NEW BUILDING MATERIALS Co.,Ltd. Address before: 250353 Science Park, West New Town University, Changqing District, Shandong, Ji'nan Patentee before: Qilu University of Technology |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20210705 Address after: Room 506, neighborhood center, Korean Industrial Park, No. 50, Jiuhuashan Road, Yancheng Economic and Technological Development Zone, Jiangsu Province, 224000 Patentee after: Yancheng Hanzi Industrial Park Industrial Development Co.,Ltd. Address before: No.18, Songjiang Road, Yancheng Economic Development Zone, Jiangsu Province 224000 Patentee before: JIANGSU CHENGTIAN NEW BUILDING MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |