CN1579935A - Method for preparing micron spherical mesoporous silicon dioxide - Google Patents
Method for preparing micron spherical mesoporous silicon dioxide Download PDFInfo
- Publication number
- CN1579935A CN1579935A CN 03153265 CN03153265A CN1579935A CN 1579935 A CN1579935 A CN 1579935A CN 03153265 CN03153265 CN 03153265 CN 03153265 A CN03153265 A CN 03153265A CN 1579935 A CN1579935 A CN 1579935A
- Authority
- CN
- China
- Prior art keywords
- concentration
- mol
- acid
- poly
- mesoporous
- 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
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention belongs to the field of semiconductor material's preparation and application technology, especially round silicon dioxide. Utilizing surfactant as template and silicate ester as silicon source, hydrolytic condensation is done under acidity condition. The invention has not only low energy consumption and a good dispersity, but also the aperture can be controlled by adding bulk agent.
Description
Invention field
The invention belongs to the preparation and the applied technical field of semiconductor material, particularly relate to the preparation method of micron-size spherical mesoporous silicon oxide.
Background technology
Mesoporous silicon oxide is a kind of of porosu solid, and it is between micropore (aperture＞2nm) and grand hole (a kind of porosu solid between the solid of aperture＞50nm).Mesoporous silicon oxide is the noticeable research object in nanometer material science field in recent years.Mesoporous solid is because huge specific surface area (is generally 1000m
2/ g) and uniform hole dimension makes it in catalysis and separation science important use be arranged, as the selectivity absorption of chromatogram, support of the catalyst, molecule, screening, catalysis etc.Mesoporous size make bigger molecule of processing or gene become may and in the great application prospect of aspects such as electronics, optics and micromechanics, particularly mesoporous solid is as the carrier of artificial heterogeneous assembly system, being about to heterogeneous nano particle (or molecule) is assembled in the hole of mesoporous solid, form mesoporous composite material, produce various new-type functional material.
Mesoporous silica molecular sieve can be by ion and neutral surface active agent's preparation, and still the mesoporous silicon oxide that obtains is easy to generate the uneven irregular coacervate of size usually.Control mesoporous silicon oxide pattern can make that mesoporous silicon oxide has new purposes at aspects such as chromatogram and catalysis.Some document relates to the synthetic of mesoporous silica spheres.The mesoporous silica spheres that under stirring, alkaline condition, can synthesize 0.1～2mm and submicron 0.4～1.1 μ m by the cats product of modification.But the mesoporous silica spheres of synthetic will be used for high performance liquid chromatography and also will be further processed [Huo, Q.; Feng, J.; Schuth, F.; Stucky, G.D.Chem.Mater. 1997,9, and 14; Grun, M.; Lauer, I.; Unger, K.K.Adv.Mater. 1997,9, and 254].After removing, organic formwork agent becomes hollow ball and easily broken [Schacht, S. by emulsion template at synthetic 1～100 μ m mesoporous silica spheres under stirring, the acidic conditions; Huo, Q.; Voigt-Martin, I.G.; Stucky, G.D.; Schuth, F.Science1996,273,768].Agnes E.Ostafin etc. adopt the mesoporous silica spheres of the synthetic 60～740nm of cats product under alkaline condition, but, be reflected in the dilute solution and carry out, productive rate lower [Robert I.Nooney, Dhanasekaran Thirunavukkarasu, Yimei Chen, Robert Josephs, and Agnes E.OstafinChem.Mater.2002,14 (11), 4721-4728].
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the sphericity mesoporous silicon dioxide of micron order scope at normal temperatures.Adopt present method technology simple, and can reduce production costs.
It is template that mesoporous silica spheres of the present invention adopts mixed surfactant, is the silicon source with the silicon ester, prepares mesoporous silicon oxide under acidic conditions, about 1～5 μ m of mean sizes size of the sphericity mesoporous silicon dioxide that obtains.
The objective of the invention is to be achieved through the following technical solutions:
Utilizing tensio-active agent to be template, is the silicon source with silicon ester, and hydrolytic condensation forms under acidic conditions.
The step of concrete grammar comprises:
(1) preparating acid solution, the concentration of acid is 0.01～10 mol, is preferably 0.1～10 mol;
(2) in the solution of step (1), add tensio-active agent, make that the concentration of cetyl trimethyl ammonium halide is 0.001～5 mol in the mixing solutions, be preferably 0.01～0.5 mol; The concentration of polyvinyl alcohol is 0.01～20 grams per liter, is preferably 0.1～20 grams per liter, and the concentration of poly-(oxygen ethene)-poly-(oxypropylene)-poly-(oxygen ethene) is 1 * 10
-6～5 * 10
-3Mol is preferably 1 * 10
-5～5 * 10
-3Mol;
(3) silicon ester is added in the mixing solutions that step (2) obtains, the concentration that makes mixed silicon ester is 0.01～5 mol, be preferably 0.05～1 mol, continue to stir 5～30 minutes, leave standstill for some time, get the solution of white precipitate, centrifugation then, washing, drying after 500～800 ℃ of roastings, obtain mesoporous silicon oxide, particle diameter is 1～5 μ m, and specific surface area is 650～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
Described acid comprises one or both mixtures of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid.
Described cetyl trimethyl ammonium halide can be cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
Described silicon ester can be methyl silicate or tetraethoxy etc.
The mesoporous silicon oxide that the inventive method is prepared is of many uses, is the mesoporous material with huge specific surface area, is widely used in the fields such as preparation of selectivity absorption, screening, catalysis and the matrix material of chromatogram, support of the catalyst, molecule.
The Metaporous silicon dioxide material that method of the present invention obtains is shown in accompanying drawing 1, accompanying drawing 2.Method of the present invention not only energy consumption is low, the product purity height, and good dispersity, and mesoporous size can be controlled by adding swelling agent.It is simple that the present invention prepares the method for Metaporous silicon dioxide material, is easy to apply.
What method of the present invention was significantly different with preparation method in the past is, in the present invention, the preparation of Metaporous silicon dioxide material is to carry out at normal temperatures, and without large-scale instrument, thereby cost is very low, is fit to scale operation.
Description of drawings
Fig. 1. the sphericity mesoporous silicon dioxide material stereoscan photograph of embodiments of the invention 1;
Fig. 2. the sphericity mesoporous silicon dioxide material stereoscan photograph of embodiments of the invention 3;
Embodiment
Embodiment 1
(1) preparation hydrochloric acid soln, the concentration of hydrochloric acid is 2.0 mol.
(2) solution of preparation tensio-active agent, adding tensio-active agent to step (1) in makes that the concentration of cetyl trimethylammonium bromide is 0.05 mol in the mixing solutions; The concentration of polyvinyl alcohol is 8.0 grams per liters; The concentration of poly-(oxygen ethene)-poly-(oxypropylene)-poly-(oxygen ethene) is 3.5 * 10
-4Mol.
(3) tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 0.50 mol, continue to stir 7 minutes, leave standstill for some time then, get the solution of white precipitate, centrifugation then, washing, drying, after 600 ℃ of roastings, obtain mesoporous silicon oxide, median size is 1.3 μ m, and specific surface area is 860m
2/ g, the mesoporous 4.4nm that is of a size of.
Embodiment 2
(1) preparation salpeter solution, the concentration of nitric acid is 6.0 mol.
(2) solution of preparation tensio-active agent, adding tensio-active agent in (1) makes that the concentration of palmityl trimethyl ammonium chloride is 0.040 mol in the solution behind the mixed dissolution; The concentration of polyvinyl alcohol is 6.0 grams per liters; The concentration of poly-(oxygen ethene)-poly-(oxypropylene)-poly-(oxygen ethene) is 6 * 10
-4Mol.
(3) tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed methyl silicate is 4.0 mol, continue to stir 15 minutes, leave standstill for some time then, get the solution of white precipitate, centrifugation then, washing, drying, after 550 ℃ of roastings, obtain mesoporous silicon oxide, median size is 2.1 μ m, and specific surface area is 920m
2/ g, the mesoporous 2.7nm that is of a size of.
Embodiment 3
With embodiment 1, change the hydrochloric acid in the step (1) into sulfuric acid, other condition is constant, obtains mesoporous silicon oxide, and median size is 3.1 μ m, and specific surface area is 1090m
2/ g, the mesoporous 2.3nm that is of a size of.
Embodiment 4
(1) preparation hydrochloric acid soln, the concentration of hydrochloric acid is 0.01 mol.
(2) solution of preparation tensio-active agent, adding tensio-active agent in (1) makes that the concentration of palmityl trimethyl ammonium chloride is 0.05 mol in the solution behind the mixed dissolution; The concentration of polyvinyl alcohol is 0.1 grams per liter; The concentration of poly-(oxygen ethene)-poly-(oxypropylene)-poly-(oxygen ethene) is 1.7 * 10
-6Mol.
(3) tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 0.05 mol, continue to stir 10 minutes, leave standstill for some time then, get the solution of white precipitate, centrifugation then, washing, drying, after 700 ℃ of roastings, obtain mesoporous silicon oxide, median size is 4.6 μ m, and specific surface area is 685m
2/ g, the mesoporous 3.4nm that is of a size of.
Claims (9)
1. the preparation method of a micron sphericity mesoporous silicon dioxide, it is characterized in that: described method steps comprises:
(1) preparating acid solution, the concentration of acid is 0.01～10 mol;
(2) in the solution of step (1), add tensio-active agent, make that the concentration of cetyl trimethyl ammonium halide is 0.001～5 mol in the mixing solutions, the concentration of polyvinyl alcohol is 0.01～20 grams per liter, and the concentration of poly-(oxygen ethene)-poly-(oxypropylene)-poly-(oxygen ethene) is 1 * 10
-6～5 * 10
-3Mol;
(3) silicon ester is added in the mixing solutions that step (2) obtains, the concentration that makes mixed silicon ester is 0.01～5 mol, continues to stir, leave standstill, the solution of white precipitate, centrifugation, washing, drying, roasting obtains mesoporous silicon oxide.
2. the method for claim 1, it is characterized in that: described mesoporous silicon oxide particle diameter is 1～5 μ m, and specific surface area is 650～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
3. the method for claim 1, it is characterized in that: described acid comprises one or both mixtures of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid.
4. the method for claim 1, it is characterized in that: described cetyl trimethyl ammonium halide is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
5. the method for claim 1, it is characterized in that: described silicon ester is methyl silicate or tetraethoxy.
6. the method for claim 1 is characterized in that: the concentration of described step (1) acid is 0.1～10 mol.
7. the method for claim 1, it is characterized in that: the concentration of the cetyl trimethyl ammonium halide of described step (2) is 0.01～0.5 mol; The concentration of polyvinyl alcohol is 0.1～20 grams per liter; The concentration of poly-(oxygen ethene)-poly-(oxypropylene)-poly-(oxygen ethene) is 1 * 10
-6～5 * 10
-3Mol.
8. the method for claim 1, it is characterized in that: the concentration of the mixing solutions mesosilicic acid ester that described step (3) obtains is 0.05～1 mol.
9. the method for claim 1, it is characterized in that: described maturing temperature is 500～800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153265 CN1239388C (en) | 2003-08-12 | 2003-08-12 | Method for preparing micron spherical mesoporous silicon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153265 CN1239388C (en) | 2003-08-12 | 2003-08-12 | Method for preparing micron spherical mesoporous silicon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1579935A true CN1579935A (en) | 2005-02-16 |
| CN1239388C CN1239388C (en) | 2006-02-01 |
Family
ID=34579989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03153265 Expired - Fee Related CN1239388C (en) | 2003-08-12 | 2003-08-12 | Method for preparing micron spherical mesoporous silicon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1239388C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500561C (en) * | 2007-05-08 | 2009-06-17 | 浙江大学 | Preparation method of size controlled hollow silicon oxide microsphere |
| CN101391776B (en) * | 2007-09-21 | 2011-01-12 | 中国科学院理化技术研究所 | Method for preparing porous silicon dioxide nano sphere with special structure on surface and porous silicon dioxide nano sphere |
| CN102398907A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Method for preparing mesoporous silicon oxide microballoons |
| CN102952218A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Alkene polymerization method |
| WO2014048060A1 (en) * | 2012-09-25 | 2014-04-03 | Tang Weizhao | Anti-inflammatory drug against cancer and aids with radiotherapy and preparation method thereof |
| CN109042637A (en) * | 2018-09-21 | 2018-12-21 | 中国科学院合肥物质科学研究院 | Preparation method, pesticide adhesive agent and the application method of higher suspension pesticide adhesive agent |
| CN110341014A (en) * | 2019-06-12 | 2019-10-18 | 李辉 | A kind of preparation method of mildew preventing agent for wood |
| WO2021243936A1 (en) * | 2020-06-05 | 2021-12-09 | 中国石油化工股份有限公司 | Sphere-like super-macroporous mesoporous material and polyolefin catalyst containing same |
| CN114455595A (en) * | 2022-02-25 | 2022-05-10 | 蚌埠学院 | Micron-sized large-size monodisperse silica microsphere and preparation method thereof |
-
2003
- 2003-08-12 CN CN 03153265 patent/CN1239388C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500561C (en) * | 2007-05-08 | 2009-06-17 | 浙江大学 | Preparation method of size controlled hollow silicon oxide microsphere |
| CN101391776B (en) * | 2007-09-21 | 2011-01-12 | 中国科学院理化技术研究所 | Method for preparing porous silicon dioxide nano sphere with special structure on surface and porous silicon dioxide nano sphere |
| CN102398907A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Method for preparing mesoporous silicon oxide microballoons |
| CN102398907B (en) * | 2010-09-08 | 2013-08-21 | 清华大学 | Method for preparing mesoporous silicon oxide microballoons |
| CN102952218A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Alkene polymerization method |
| CN102952218B (en) * | 2011-08-25 | 2014-08-06 | 中国石油化工股份有限公司 | Alkene polymerization method |
| WO2014048060A1 (en) * | 2012-09-25 | 2014-04-03 | Tang Weizhao | Anti-inflammatory drug against cancer and aids with radiotherapy and preparation method thereof |
| CN109042637A (en) * | 2018-09-21 | 2018-12-21 | 中国科学院合肥物质科学研究院 | Preparation method, pesticide adhesive agent and the application method of higher suspension pesticide adhesive agent |
| CN110341014A (en) * | 2019-06-12 | 2019-10-18 | 李辉 | A kind of preparation method of mildew preventing agent for wood |
| WO2021243936A1 (en) * | 2020-06-05 | 2021-12-09 | 中国石油化工股份有限公司 | Sphere-like super-macroporous mesoporous material and polyolefin catalyst containing same |
| CN114455595A (en) * | 2022-02-25 | 2022-05-10 | 蚌埠学院 | Micron-sized large-size monodisperse silica microsphere and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1239388C (en) | 2006-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1239388C (en) | Method for preparing micron spherical mesoporous silicon dioxide | |
| CN100335567C (en) | calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method | |
| CN108609649B (en) | Preparation method of sea urchin-shaped magnetic hollow microspheres | |
| CN102295298B (en) | Method for synthesizing mesoporous silica molecular sieve | |
| CN1244492C (en) | Synthesis method of monodispersed nano-mesopore silicon dioxide material | |
| CN108543505A (en) | A kind of compound particle and preparation method thereof with multiple nucleocapsid | |
| WO2001009035A1 (en) | Molecularly-imprinted material made by template-directed synthesis | |
| CN108579705B (en) | Preparation method of mesoporous silica microspheres | |
| CN1730392A (en) | Large aperture capacity silicon oxide vesicle, foamed material and process for preparing the same | |
| CN1966141A (en) | Preparation method of ferro-doped TiO2/SiO2 aerogel microball | |
| CN1654324A (en) | Method for preparing SiO2 aerogel with nanometer apertures under normal pressure | |
| CN1278931C (en) | Process for continuously preparing meso visual ordered hybridization silicon dioxide fiber | |
| CN1264747C (en) | Columnar mesoporous silicon dioxide and its preparing method | |
| CN1486929A (en) | Prepn of mesoporous spherical nano Sio2 particle | |
| CN1868581A (en) | Method for preparing TiO2/SiO2 aerogel microsphere | |
| CN1299984C (en) | Method for synthesizing micron spherical mesoporous SiO2 using silicate as silicon source | |
| CN1730389A (en) | Ultrasonic method for synthesizing mesoporous monox nanometer ball carrier material | |
| CN1120801C (en) | Dual-pore molecular sieve and its preparing process | |
| CN1244493C (en) | Preparation method of monodispersed nano-mesopore molecular sieve | |
| CN109718744A (en) | A kind of hollow crinosity ball of Janus, Preparation method and use | |
| CN1669921A (en) | Method for preparing silicon dioxide aerogel by normal pressure drying method using rice hull ash as raw material | |
| CN102583404A (en) | Mesoporous silicon dioxide nanometer particle and preparation method | |
| CN1730390A (en) | Process for preparing monox mesoporous material with helical structure | |
| CN1772607A (en) | Ultrasonic treating process of preparing spherical nanometer silica particle | |
| CN109865496A (en) | Magnetic silica filler, magnetic affine filler and preparation method and purposes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060201 Termination date: 20170812 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |